Non-newtonian colloidal disperse system



United States Patent C) US. Cl. 252-33 16 Claims ABSTRACT OF THEDISCLOSURE Compositions characterized by improved rheological propertiescomprising a material capable of possessing thixotropic or pseudoplasticproperties and non-Newtonian colloidal disperse systems. These systemsare characterized as colloidal dispersions of solid, metal-containingcolloidal particles predispersed in an inert organic liquid and, as anessential third component of the system, an organic compound withmolecules which contain a hydrophobic portion and at least onepolarsubstituent. A typical composition contains polyvinylchloride polymer, aplasticizer for the polymer, and a disperse system comprising calciumcarbonate particles, a liquid hydrocarbon dispersing medium, and acalcium petrosulfonate. A method for imparting improved rheologicalproperties to materials susceptible to possessing such properties byincorporating therein these disperse systems is described as are novelnon-Newtonian disperse systems per se described in detail.

This application is a continuation-in-part of earlier filed applicationsSer. No. 185,521, filed Apr. 6, 1962, now Patent No. 3,242,079; Ser. No.309,293, filed Sept. 16, 1963, now abandoned; Ser. No. 323,135, filedNov. 12, 1963, now abandoned; Ser. No. 369,271, filed May 21, 1964, nowabandoned; Ser. No. 535,048, filed Mar. 17, 1966, now abandoned; Ser.No. 535,693, now Patent No. 3,372,115 filed Mar. 21, 1966; Ser. No.535,742, filed Mar. 21, 1966, now abandoned; Ser. No. 580,575, nowPatent No. 3,376,222 filed Sept. 20, 1966; and Ser. No. 612,332, nowPatent No. 3,384,586 filed Jan. 30, 1967.

This invention relates to compositions characterized by non-Newtonianrheological properties. In particular, the invention concerns resinouscompositions comprising as an essential constituent a non-Newtoniancolloidal disperse system in intimate admixture with the remainingingredients of the composition and to methods for making suchcompositions. In another aspect, the invention relates to novelnon-Newtonian colloidal disperse systems.

It is well known in the art that many applications of resinouscompositions and other materials such as lubricants, greases, sealants,fillers, adhesives, etc., require that the compositions possess certainrheological characteristics. Specifically, it is desirable that the rateof fiow of the compositions be dependent upon the rate of shear, i.e.,strain. Thus, the apparent viscosity of such compositions depends uponthe rate of shear. At low rates of shear, the viscosity of thecomposition appears high but as the rate of shear applied to thecompositions increases, the apparent viscosity decreases.

The particular type of non-Newtonian flow characteristics possessed bythe resinous compositions of the present invention are characterized asthixotropic and pseudoplastic. The apparent viscosity of the thixotropiccomposition depends on both the rate of shear and the length of time inwhich a shearing action is applied. A pseudoplastic composition has anapparent viscosity which is low at high rates of shear but which appearshigher as the rate of shear decreases. Its viscosity is,- however,independent of the duration of the shearing action. The rheologicalcharacteristics of materials are discussed further in many standardtexts such as: B. Jirgensons and M. E. Strau'manis, A Short Textbook onColloidal Chemistry (2nd Ed), The Macmillan Co., N.Y., 1962,particularly pages 178 through 183.

Thixotropic and pseudoplastic properties are obviously important in manycompositions containing polymeric resins such as paints, greases,caulks, coatings, molding compositions, extruding compositions, and thelike. For example, paints should flow sufliciently under the pressure ofa brush in order to cover the surface involved. Yet, the paint mustremain sufficiently thick or viscous to prevent precipitation of thepigment during storage and prior to drying and to stop the paint fromflowing after the pressure of the brush is removed. Similarly, when articles are coated by dipping them into resinous compositions, it isimportant that the apparent viscosity of the compositions decrease asthe result of the mechanical action associated with lowering the articleinto the composition. However, upon removal, the material coated on thearticle is no longer subject to any mechanical action and should becomemore viscous to avoid sagging or further flowing of the coating over thesurface. When extruding various plastic compositions, it is desirablethat the flow rate for the plastic increase under the force of theextruder screw but the flow rate should decrease rapidly after exitingthe extruder so that the article retains its shape. Moreover, thedifference in apparent viscosity of materials during extrusion and afterexiting the extruder is a factor in determining the maximum satisfactoryextrusion speeds, an important economic consideration in the plasticsindustry.

These are but a few of the many applications of resinous compositionscharacterized by pseudoplastic or thioxtropic flow characteristics. Manyother uses are known to those skilled in the art and need no additionalelaboration herein.

In accordance with the foregoing, it is a principal object of theinvention to provide novel non-Newtonian compositions.

Another object is to provide novel compositions characterized bypseudoplastic or thixotropic flow properties.

A further object is to provide resinous compositions comprising an anessential constituent a non-Newtonian colloidal disperse system inintimate admixture with other constituents in the composition.

Another object is to provide resinous compositions containing as anessential ingredient a colloidal disperse system capable of impartingpseudoplastic, thixotropic, and lubricating properties to thecomposition.

A still further object is to provide a method for impartingpseudoplastic or thixotropic properties to materials capable ofpossessing such properties by intimately admixing therewith an eifectiveamount of a non-Newtonian colloidal disperse system.

An additional object of the invention is to provide a process forpreparing the novel resinous compositions of this invention.

A further object is to provide novel non-Newtonian colloidal dispersesystems and methods for their preparation.

These and other objects of the invention are achieved by providing aresinous composition comprising an intimate mixtures of (A) a polymericresin and (B) a non- Newtonian colloidal disperse system comprising (1)solid metal-containing colloidal particles predispersed in (2) adisperse medium of at least one inert, organic liquid, and (3) as anessential third component at least one member selected from the classconsisting of organic compounds which are substantially soluble in saiddisperse medium, the molecules of said organic compound beingcharacterized by polar substituents and hydrophobic portions. Thepolymeric resins and the colloidal disperse system which comprise theessential ingredients of the resinous composition of the invention arediscussed more fully hereinafter. By substituting for all or part of theresin another material which is susceptible to possessing thixotropic orpseudoplastic properties (e.g., greases, lubricants, gels, sealants,caulks, fillers, adhesives, etc.), other compositions falling within thescope of the present invention can be prepared.

THE POLYMERIC RESIN Representative classes of suitable polymeric resinsuseful in the compositions of the invention include polyolefins,polyamides, acrylics, polystyrenes, polysulfides, polyethers,polyfluorocarbons, polymercaptans, polyesters, polyurethanes, acetalresins, polyterpenes, phenolics, cellulosics, melamine resins, furaneresins, alkyd resins, silicone resins, natural resins, mixtures ofnatural resins, mixtures of synthetic resins, mixtures of natural andsynthetic resins, and the like. These classes of resins are well knownas evidenced by such prior art as Modern Plastics (Encyclopedia Issue),vol. 38, No. 1A, September 1960, published by Breskins Publications,Inc., Bristol, Conn. This publication sets forth many illustrativeexamples falling within the above classes of resins as well as othersuitable polymeric materials.

More specifically, representative examples of the many suitablepolymeric resin, compositions include the following: polyacrylic acids,polymethacrylic acids, poly-2- halo-acrylic acids, poly-2-cyanoacrylicacids, and the corresponding polyesters of these acids wherein thealcoholic moiety is derived from (1) alkanols of one to about twentycarbon atoms, e.g., methanol, ethanol, butanol, octanol, lauryl alcohol,stearyl alcohol, ethylene glycol, polyethylene glycol; (2) haloalkanolssuch as Z-chloroethanol; (3) aminoalkanols, e.g., 2-(tert-butylamino)-ethanol and 2-diethylaminoethanol; (4) alkoxy alkanols exemplified by2-methoxy-ethanol, Z-ethoxy-ethanol, and 3-ethoxy-propanol; and (5)cycloalkanols such as cyclohexanol and cyclopropanol; the correspondingpolyamides of these acids including alkylene bis-amides and other N-substituted amides such as N-tert-butylacrylamide; polyacrylonitrile,and acrylic resins derived from the copolymerization of two or more ofthese acrylic monomers, i.e., acrylic acid, acrylonitrile, methacrylicacid, 2-chloroacrylic acid, Z-cyanoacrylic acid, and the correspondingamides and esters of these acids. Polymers and copolymers of theN-3-oxohydrocarbon substituted acrylamides of the type disclosed in US.Patent 3,277,056 are also contemplated.

Other suitable polymeric resins include cellulosics such as cellulosenitrates, cellulose acetates, cellulose propionates, cellulosebutyrates, ethylcellulose; and combinations of these such as celluloseacetate butyrate; poiyolefins exemplified by polyethylene,polypropylene, polybutenes, polyisobutylenes, ethylene-propylenecopolymers, ethylene-propylene copolymers including up to about 3% of adiolefin; polyhalo olefins, e.g., polytetrafiuorocthylenes,polychlorotrifiuoroethylenes; polyamides including polycaprolactams,polyamides derived from sebacic and/or adipic acid and alkylenepolyamines such as hexamethylene diamine; the polyamide derived from thepolymerization of ll-amino undecanoic acid; polystyrene; polystyrene andstyrene containing copolymers and terpolymers such as copolymers ofstyrene and acrylonitrile or terpolymers of styrene, 1,3-butadiene, andacrylonitrile; the chlorinated polyether derived from opening achlorinated oxetane ring prepared from pentaerythritol, e. g., thepolyether sold under the name Penton by Hercules Powder Co.

Still other suitable resins, include the polymers and copolymers ofvinyl chloride, vinylidene chloride, and vinyl esters such as vinylacetate; polyvinyl acetals such 4 as polyvinyl acetal per se andpolyvinyl butyral; urea formaldehyde resins; melamine-formaldehyderesins; coumarone-indene resins; phenol-formaldehyde resins;phenol-furfural resins; and the like. Various mixtures of these resinscan also be utilized in the compositions of the invention.

The resinous compositions contemplated by the present invention includedispersion resins, i.e., (1) plastisols, (2) organosols, and (3)modified plastisols such as plasticized resins exemplified byplasticized polyvinyl chloride, polyvinyl acetate, cellulose acetates,cellulose nitrates, and the like. The colloidal disperse systems arereadily incorporated into these liquid compositions simply by mixing.The terms plastisol, organsosol, and modified plastisol are terms of artused to describe various liquid resinous materials in the form ofsuspensions or solutions of powdered or pelletized resins in variousplasticizers, diluents, dispersants, solvents, etc. (See ModernPlastics, supra, pages l30131, 4l3415.) In fact, these dispersion resincompositions are a preferred class of polymeric resins in which toemploy the colloidal disperse systems.

Plasticizers which can be utilized in the resinous compositions of thisinvention include phthalates, phosphates, adipates, azelates, sebacates,and the like. Specific examples are the dialkyl phthalates such asdi(2-ethylhexyl)-phthalates, dibutyl phthalate, diethyl phthalate,dioctyl phthalate, butyl octyl phthalate; dicyclohexyl phthalate, butylbenxyl phthalate; triaryl phosphates such as tricresyl phosphate,triphenyl phosphate, cresyldiphenyl phosphate; trialkyl phosphates suchas trioctyl phosphate and tributyl phosphate; alkoxyalkyl phosphatessuch as tributoxyethyl phosphate; alkylaryl phosphates such as octyldiphenyl phosphate; alkyl adipates such as di-(2-ethylhexyl)adipate,diisooctyl adipate, octyl decyl adipate; dialkyl sebacates such asdibutyl sebacate, dioctyl sebacate, diisooctyl sebacate; alkyl azelatessuch as di(2-ethylhexyl)azelate and di-(Z-ethylbutyl) azelate; and thelike. Other plasticizers include citrates such as acetyl tri-n-butylcitrate, acetyl triethyl citrate, monoisopropyl citrate, triethylcitrate, mono-, di,- and tri-stearyl citrate; triacetin, p-tert-butylphenyl salicylate, butyl stearate; benzoic acid esters derived fromdiethylene glycol, dipropylene glycol, triethylene glycol, andpolyethylene glycols; sulfonamides such as toluenesulfonamide, etc. Alisting of illustrative suitable plasticizers is found o pages 413through 416 and 648 to 664 of the above-cited volume of Modern Plastics.

The amount of plasticizer employed, if one is employed, will depend onthe nature of the polymeric resin and the plasticizer. However, asreadily shown by reference to the cited portions of Modern Plastics, theuse of plasticized resins is conventional and the selection of anappropriate type and amount of plasticizer or mixture of plasticizersfor a particular polymeric resin or mixture of resins is well within theskill of the art.

THE COLLOIDAL DISPERSE SYSTEMS The terminology disperse system as usedin the speci fication and claims is a term of art generic to colloids orcolloidal solutions, e.g., any homogeneous medium containing dispersedentities of any size and state, Jirgensons and Straurnanis, page 1,supra. However, the par ticular disperse systems of the presentinvention form a subgenus within this broad class of disperse system,this subgenus being characterized by several important features.

This subgenus comprises those disperse systems wherein at least aportion of the particles dispersed therein are solid, metal-containingparticles formed in situ. At least about 10% to about 50% are particlesof this type and preferably, substantially all of said solid particlesare formed in situ.

So long as the solid particles remain dispersed in the dispersing mediumas colloidal particles the particle size is not critical. Ordinarily,the particles will not exceed 5000 A. However, it is preferred that themaximum unit particle size be less than about 1000 A. In a particularlypreferred aspect of the invention, the unit particle size is less thanabout 400 A. Systems having a unit particle size in the range of 30 A.to 200 A. give excellent results. The minimum unit particle size is atleast A. and preferably at least about 30 A.

The language unit particle size is intended to designate the averageparticle size of the solid, metalcontaining particles assuming maximumdispersion of the individual particles throughout the disperse medium.That is, the unit particle is that particle which corresponds in size tothe average size of the metal-containing particles and is capable ofindependent existence within the disperse system as a discrete colloidalparticle. These metalcontaining particles are found in two forms in thedisperse systems. Individual unit particles can be dispersed as suchthroughout the medium or unit particles can form an agglomerate, incombination with other materials (e.g., another metal-containingparticle, the disperse medium, etc.) which are present in the dispersesystems. These agglomerates are dispersed through the system asmetalcontaining particles. Obviously, the particle size of theagglomerate is substantially greater than the unit particle size.Furthermore, it is equally apparent that this agglomerate size issubject to wide variations, even within the same disperse system. Theagglomerate size varies, for example, with the degree of shearing actionemployed in dispersing the unit particles. That is, mechanical agitationof the disperse system tends to break down the agglomerates into theindividual components thereof and disperse these individual componentsthroughout the disperse medium. The ultimate in dispersion is achievedwhen each solid, metal-containing particle is individually dispersed inthe medium. Accordingly. the disperse systems are characterized withreference to the unit particle size, it being apparent to those skilledin the art that the unit particle size represents the average size ofsolid, metal-containing particles present in the system which can existindependently. The average particle size of the metal-containing solidparticles in the system can be made to approach the unit particle sizevalue by the application of a shearing action to the existent system orduring the formation of the disperse system as the particles are beingformed in situ. It is not necessary that maximum particle dispersionexist to have useful disperse systems. The agitation associated withhomogenization of the overbased material and conversion agent producessufificient particle dispersion.

Basically, the solid metal-containing particles are in the form of metalsalts of inorganic acids and low molecular weight organic acids,hydrates thereof, or mixtures of these. These salts are usually thealkali and alkaline earth metal formates, acetates, carbonates, hydrogencarbonates, hydrogen sulfides, sulfites, hydrogen sulfites, and halides,particularly chlorides. In other words, the metal-containing particlesare ordinarily particles of metal salts, the unit particle is theindividual salt particle and the unit particle size is the averageparticle size of the salt particles which is readily ascertained, as forexample, by conventional X-ray diffraction techniques. Colloidaldisperse systems possessing particles of this type are sometimesreferred to as macromolecular colloidal systems.

Because of the composition of the colloidal disperse systems of thisinvention, the metal-containing particles also exist as components inmicellar colloidal particles. In addition to the solid metal-containingparticles and the disperse medium, the colloidal disperse systems of theinvention are characterized by a third essential component, one which issoluble in the medium and contains in the molecules thereof ahydrophobic portion and at least one polar substituent. This thirdcomponent can orient itself along the external surfaces of the abovemetal salts, the polar groups lying along the surface of these saltswith the hydrophobic portions extending from the salts into the dispersemedium forming micellar colloidal particles. These micellar colloids areformed through weak intermolecular forces, e.g., Van der Waals forces,etc. Miscellar colloids represent a type of agglomerate particle asdiscussed thereinabove. Because of the molecular orientation in thesemicellar colloidal particles, such particles are characterized by ametal containing layer (i.e., the solid metal-containing particles andany metal present in the polar substituent of the third component, suchas the metal in a sulfonic or carboxylic acid salt group), a hydrophobiclayer formed by the hydrophobic portions of the molecules of the thirdcomponent and a polar layer bridging said metal-containing layer andsaid hydrophobic layer, said polar bridging layer comprising the polarsubstituents of the third component of the system, e.g., the

group if the third component is an alkaline earth metal petrosulfonate.

The second essential component of the colloidal disperse system is thedispersing medium. The identity of the medium is not a particularlycritical aspect of the invention as the medium primarily serves as theliquid vehicle in which solid particles are dispersed. The dispersemedium will normally consist of inert organic liquids, that is, liquidswhich are chemically substantially inactive in the particularenvironment in question (the resinous composition). While many of theseinert organic liquids are nonpolar, this is not essential. For example,many of the plasticizers for the resinous components of the compositionare esters, etc. These polar materials can also be used as thedispersing medium or components thereof. The medium can have componentscharacterized by relatively low boiling points, e.g., in the range of 25to C. to facilitate subsequent removal of a portion or substantially allof the medium from the polymeric resin composition or the components canhave a higher boiling point to protect against removal from the resinouscomposition upon standing or heating. Obviously, there is no criticalityin an upper boiling point limitation on these liquids.

Representative liquids include the alkanes and haloalkanes of five toeighteen carbons, polyhaloand perhaloalkanes of up to about six carbons,the cycloalkanes of five or more carbons, the corresponding alkyland/orhalo-substituted cycloalkanes, the aryl hydrocarbons, the alkylarylhydrocarbons, the haloaryl hydrocarbons, ethers such as dialkyl ethers,alkyl aryl ethers, cycloalkyl ethers, cycloalkylalkyl ethers, alkanols,alkylene glycols, polyalkylene glycols, alkyl ethers of alkylene glycolsand polyalkylene glycols, dibasic alkanoic acid diesters, silicateesters, and mixtures of these. Specific examples include petroleumether, Stoddard Solvent, pentane, hexane, octane, isooctane, undecane,tetradecane, cyclopentane, cyclohexane, isopropylcyclohexane,1,4-dimethylcyclohexane, cyclooctane, benzene, toluene, xylene, ethylbenzene, tert-butyl-benzene, halobenzenes especially monoandpolychlorobenzenes such as chlorobenzene per se and 3,4-dichlorotoluene,mineral oils, n-propylether, isopropylether, isobutylether, n-amylether,methyl-n-amylether, cyclohexylether, ethoxycyclohexane, methoxybenzene,isopropoxybenzene, p-methoxytoluene, methanol, ethanol, propanol,isopropanol, hexanol, n-octyl alcohol, n-decyl alcohol, alkylene glycolssuch as ethylene gycol and propylene glycol, diethyl ketone, dipropylketone, methylbutyl ketone, acetophenone,1,Z-ditluoro-tetrachloroethane, dichlorofluoromethane,1,2-dibromotetrafiuor0- ethane, trichlorofluoromethane, l-chloropentane,l,3-dichlorohexane, formamide, dimethylformamide, acetamide,dimethylacetamide diethylacetamide, propionamide, diisooctyl azelate,ethylene glycol, polypropylene glycols, hexa-l-ethylbutoxy disiloxane,etc.

Also useful as dispersing medium are the low molecular weight, liquidpolymers, generally classified as oligomers, which include the dimers,tetramers, pentamers, etc. Illustrative of this large class of materialsare such liquids as the propylene tetramers, isobutylene dimers, and thelike.

From the standpoint of availability, cost, and performance, the alkyl,cycloalkyl, and aryl hydrocarbons represent a preferred class ofdisperse mediums. Liquid petroleum fractions represent another preferredclass of disperse mediums. Included within these preferred classes arebenzenes and alkylated benzenes, cycloalkanes and alkylatedcycloalkanes, cycloalkenes and alkylated cycloalkenes such as found innaphthene-based petroleum fractions, and the alkanes such as found inthe parafiinbased petroleum fractions. Petroleum ether, naphthas,mineral oils, Stoddard Solvent, toluene, xylene, etc., and mixturesthereof are examples of economical sources of suitable inert organicliquids which can function as the disperse medium in the colloidaldisperse systems of the present invention.

The most preferred disperse systems are those containing at least somemineral oil as a component of the disperse medium. These systems areparticularly effective as lubricants for the polymeric composition, animportant feature in extrusion processes. Any amount of mineral oil isbeneficial in this respect. However, in this preferred class of systems,it is desirable that mineral oil comprise at least about 1% by Weight ofthe total medium, and preferably at least about 5% by weigth. Thosemediums comprising at least by weight mineral oil are especially useful.As will be seen hereinafter, mineral oil can serve as the exclusivedisperse medium.

In addition to the solid, metal-containing particles in the dispersemedium, the two essential elements of any disperse system, the dispersesystems employed in the polymeric compositions of the invention requirea third essential component. This third component is an organic compoundwhich is soluble in the disperse medium, and the molecules of which arecharacterized by a hydrophobic portion and at least one polarsubstituent. As

explained, infra, the organic compounds suitable as a third componentare extremely diverse. These compounds are inherent constituents of thedisperse systems as a result of the methods used in preparing thesystems. Further characteristics of the components are apparent from thefollowing discussion of methods for preparing the colloidal dispersesystems.

PREPARATION OF THE DISPERSE SYSTEMS Broadly speaking, the colloidaldisperse systems of the invention are prepared by treating a singlephase homogeneous, Newtonian system of an overbased, super based, orhyperb-ased, organic compound with a conversion agent, usually an activehydrogen containing compound, the treating operation being simply athorough mixing together of the two components, i.e., homogenization.This treatment converts these single phase systems into thenon-Newtonian colloidal disperse systems utilized in conjunction withthe polymeric resins of the present invention.

The terms overbased," superbased, and hyperbased, are terms of art whichare generic to well known classes of metal-containing materials whichhave generally been employed as detergents and/or dispersants inlubricating oil compositions. These overbased materials have also beenreferred to as complexes, metal complexes, high-metal containing salts,and the like. Overbased materials are characterized by a metal contentin excess of that which would be present according to the stoichiometryof the metal and the particular organic compound reacted with the metal,e.g., a carboxylic or sulfonic acid. Thus, if a monosulfonic acid,

is neutralized with a basic metal compound, e.g., calcium hydroxide, thenormal metal salt produced will contain one equivalent of calcium foreach equivalent of acid, i.e.,

However, as is well known in the art, various processes are availablewhich result in an inert organic liquid solution of a product containingmore than the stoichiometric amount of metal. The solutions of theseproducts are referred to herein as overbased materials. Following theseprocedures, the sulfonic acid or an alkali or alkaline earth metal saltthereof can be reacted with a. metal base and the product will containan amount of metal in excess of that necessary to neutralize the acid,for example, 4.5 times as much metal as present in the normal salt or a.metal excess of 3.5 equivalents. The actual stoichiometric excess ofmetal can vary considerably, for example, from about 0.1 equivalent toabout 30 or more equivalents depending on the reactions, the processconditions, and the like. These overbased materials useful in preparingthe disperse systems will contain from about 3.5 to about 30 or moreequivalents of metal for each equivalent of material which is overbased.

In the present specification and claims the term overbased is used todesignate materials containing a stoichiometric excess of metal and is,therefore, inclusive of those materials which have been referred to inthe art as overbased, superbased, hyperbased, etc., as discussed supra.The terminology metal ratio is used in the prior art and herein todesignate the ratio of the total chemical equivalents of the metal inthe overbased material (e.g., a metal sulfonate or car-boxylate) to thechemical equivalents of the metal in the product which would be expectedto result in the reaction between the organic material to be overbased(e.g., sulfonic or carboxylic acid) and the metal-containing reactant(e.g., calcium hydroxide, barium oxide, etc.) according to the knownchemical reactivity and stoichiometry of the two reactants. Thus, in thenormal calcium sulfonate discussed above, the metal ratio is one, and inthe overbased sulfonate, the metal ratio is 4.5. Obviously, if there ispresent in the material to be overbased more than one compound capableof reacting with the metal, the metal ratio of the product will dependupon whether the number of equivalents of metal in the overbased productis compared to the number of equivalents expected to be present for agiven single component or a combination of all such components.

Generally, these overbased materials are prepared by treating a reactionmixture comprising the organic material to be overbased, a reactionmedium consisting essentially of at least one inert, organic solvent forsaid organic material, a stoichiometric excess of a metal base, and apromoter with an acidic material. The methods for preparing theoverbased materials as well as an extremely diverse group of overbasedmaterials are well known in the prior art and are disclosed, for examplein the following US. patents: 2,616,904; 2,616,905; 2,616,906;2,616,911; 2,616,924; 2,616,925; 2,617,049; 2,695,910; 2,723,234;2,723,235; 2,723,236; 2,760,970; 2,767,164; 2,767,209; 2,777,874;2,798,852; 2,839,470; 2,856,359; 2,859,360; 2,856,361; 2,861,951;2,883,340; 2,915,517; 2,959,551; 2,968,642; 2,971,014; 2,989,463;3,001,981; 3,027,325; 3,070,581; 3,108,960; 3,147,232; 3,133,019;3,146,201; 3,152,991; 3,155,616; 3,170,880; 3,170,881; 3,172,855;3,194,823; 3,223,630; 3,232,883; 3,242,079;

3,242,080; 3,250,710; 3,256,136; 3,274,135. These patents discloseprocesses, materials which can be overbased, suitable metal bases,promoters, and acidic materials, as well as a variety of specificoverbased products useful in producing the disperse systems of thisinvention and are, accordingly, incorporated herein by reference.

An important characteristic of the organic materials which are overbasedis their solubility in the particular reaction medium utilized in theoverbasing process. As the reaction medium used previously has normallycomprised petroleum fractions, particularly mineral oils, these organicmaterials have generally been oilsoluble. However, if another reactionmedium is employed (e.g. aromatic hydrocarbons, aliphatic hydrocarbons,kerosene, etc.) it is not essential that the organic material be solublein mineral oil as long as it is soluble in the given reaction medium.Obviously, many organic materials which are soluble in mineral oils willbe soluble in many of the other indicated suitable reaction mediums. Itshould be apparent that the reaction medium usually becomes the dispersemedium of the colloidal disperse system or at least a component thereofdepending on whether or not additional inert organic liquid is added aspart of the reaction medium or the disperse medium.

Materials which can be overbased are generally oilsoluble organic acidsincluding phosphorus acids, thiophosphorus acids, sulfur acids,carboxylic acids, thiocarboxylic acids, and the like, as well as thecorresponding alkali and alkaline earth metal salts thereof.Representative examples of each of these classes of organic acids aswell as other organic acids, e.g., nitrogen acids, arsenic acids, etc.are disclosed along with methods of preparing overbased productstherefrom in the above cited patent and are, accordingly, incorporatedherein by reference. Patent 2,777,874 identified organic acids suitablefor preparing overbased materials which can be converted to dispersesystems for use in the resinous compositions of the invention.Similarly, 2,616,904; 2,695,910; 2,767,164; 2,767,209; 3,147,232;3,274,135; etc. disclose a variety of organic acids suitable forpreparing overbased materials as well as representative examples ofoverbased products prepared from such acids. Overbased acids wherein theacid is a phosphorus acid a thiophosphorus acid, phosphorus acid-sulfuracid combination, and sulfur acid prepared from polyolefins aredisclosed in 2,883,340; 2,915,517; 3,001,981; 3,108,960; and 3,232,883.Overbased phenates are disclosed in 2,959,551 while overbased ketonesare found in 2,798,852. A variety of overbased materials derived fromoil-soluble metal-free, nontautomeric neutral and basic organic polarcompounds such as esters, amines, amides, alcohols, ethers, sulfides,sulfoxides, and the like are disclosed in 2,968,642; 2,971,014; and2,989,463. Another class of materials which can be overbased are theoil-soluble, nitro-substituted aliphatic hydrocarbons, particularlynitro-substituted polyolefins such as polyethylene, polypropylene,polyisobutylene, etc. Materials of this type are illustrated in2,959,551. Likewise, the oil-soluble reaction product of alkylenepolyamines such as propylene diamine or N-alkylated propylene diaminewith formaldehyde or formaldehyde producing compound (e.g.,paraformaldehyde) can be overbased. Other compounds suitable foroverbasing are disclosed in the above-cited patents or are otherwisewell-known in the art.

The organic liquids used as the disperse medium in the colloidaldisperse system can be used as solvents for the overbasing process.

The metal compounds used in preparing the overbased materials arenormally the basic salts of metals in Group I-A and Group II-A of thePeriodic Table although other metals such as lead, zinc, manganese, etc.can be used in the preparation of overbased materials. The anionicportion of the salt can be hydroxyl, oxide, carbonate, hydrogencarbonate, nitrate, sulfite, hydrogen sulfite, halide, amide, sulfateetc. as disclosed in the abovecited patents. For purposes of thisinvention the preferred overbased materials are prepared from thealkaline earth metal oxides, hydroxides, and alcoholates such as thealkaline earth metal lower alkoxides. The most preferred dispersesystems of the invention are made from overbased materials containingcalcium and/or barium as the metal.

The promoters, that is, the materials which permit the incorporation ofthe excess metal into the overbased material, are also quite diverse andwell known in the art as evidenced by the cited patents. A particularlycomprehensive discussion of suitable promoters is found in 2,777,874;2,695,910; and 2,616,904. These include the alcoholic and phenolicpromoters which are preferred. The alcoholic promoters include thealkanols of one to about twelve carbon atoms such as methanol, ethanol,amyl alcohol, octanol, isopropanol, and mixtures of these and the like.Phenolic promoters include a variety of hydroxy-substituted benzenes andnaphthalenes. A particularly useful class of phenols are the alkylatedhenols of the type listed in 2,777,874, e.g., heptylphenols,octylphenols, and nonylphenols. Mixtures of various promoters aresometimes used.

Suitable acidic materials are also disclosed in the above cited patents,for example, 2,616,904. Included within the known group of useful acidicmaterials are liquid acids such as formic acid, acetic acid, nitricacid, sulfuric acid, hydrochloric acid, hydrobromic acid, carbamic acid,substituted carbamic acids, etc. Acetic acid is a very useful acidicmaterial although inorganic acidic materials such as HCl, S0 S0 CO H S,N 0 etc., are ordinarily employed as the acidic materials. The mostpreferred acidic materials are carbon dioxide and acetic acid.

In preparing overbased materials, the material to be overbased, aninert, non-polar, organic solvent therefor, the metal base, thepromoter, and the acidic material are brought together and a chemicalreaction ensues. The exact nature of the resulting overbased product isnot known. However, it can be adequately described for purposes of thepresent specification as a single phase homogeneous mixture of thesolvent and (1) either a metal complex formed from the metal base, theacidic material, and the material being overbased and/or (2) anamorphous metal salt formed from the reaction of the acidic materialwith the metal base and the material which is said to be overbased.Thus, if mineral oil is used as the reaction medium, petrosulfonic acidas the material which is overbased, Ca(OH) as the metal base, and carbondioxide as the acidic material, the resulting overbased material can bedescribed for purposes of this invention as an oil solution of either ametal containing complex of the acidic material, the metal base, and thepetrosulfonic acid or as an oil solution of amorphous calcium carbonateand calcium petrosulfonate. Since the overbased materials are wellknownand as they are used merely as intermediates in the preparation of thedisperse systems employed herein, the exact nature of the materials isnot critical to the present invention.

The temperature at which the acidic material is contacted with theremainder of the reaction mass depends to a large measure upon thepromoting agent used. With a phenolic promoter, the temperature usuallyranges from about C. to 300 C., and preferably from about C. to about200 C. When an alcohol or mercaptan is used as the promoting agent, thetemperature usually will not exceed the reflux temperature of thereaction mixture and preferably will not exceed about 100 C.

In view of the foregoing, it should be apparent that the overbasedmaterials may retain all or a portion of the promoter. That is, if thepromoter is not volatile (e.g., an alkyl phenol) or otherwise readilyremovable from the overbased material, at least some promoter remains inthe overbased product. Accordingly, the disperse systems made from suchproducts may also contain the promoter. The presence or absence of thepromoter in the overbased material used to prepare the disperse systemand likewise, the presence or absence of the promoter in the colloidaldisperse systems themselves does not represent a critical aspect of theinvention. Obviously, it is within the skill of the art to select avolatile promoter such as a lower alkanol, e.g., methanol, ethanol,etc., so that the promoter can be readily removed prior to forming thedisperse system or thereafter.

A preferred class of overbased materials used as starting materials inthe preparation of the disperse systems of the present invention are thealkaline earth metal-overbased oil-soluble organic acids, preferablythose containing at least twelve aliphatic carbons although the acidsmay contain as few as eight aliphatic carbon atoms if the acid moleculeincludes an aromatic ring such as phenyl, naphthyl, etc. Representativeorganic acids suitable for preparing these overbased materials arediscussed and identified in detail in the above-cited patents.Particularly 2,616,- 904 and 2,777,874 disclose a variety of verysuitable organic acids. For reasons of economy and performance,overbased oil-soluble carboxylic and sulfonic acids are particularlysuitable. Illustrative of the carboxylic acids are palmitic acid,stearic acid, myristic acid, oleic acid, linoleic acid, behenic acid,hexatriacontanoic acid, tetrapropylone-substituted glutaric acid,polyisobutene (M.W. 5000)-substituted succinic acid, polypropylene,(M.W. 10,000)-substituted succinic acid, octadecyl-substituted adipicacid, chlorostearic acid, 9-methylstearic acid, dichlorostearic acid,stearylbenzoic acid, eicosane-substituted naphthoic acid,dilauryl-decahydro-naphthalene carboxylic acid, didodecyl-tetralincarboxylic acid, clioctylcyclohexane carboxylic acid, mixtures of theseacids, their alkali and alkaline earth metal salts, and/or theiranhydrides. Of the oil-soluble sulfonic acids, the mono-, di-, andtrialiphatic hydrocarbon substituted aryl sulfonic acids and thepetroleum sulfonic acids (petrosulfonic acids) are particularlypreferred. Illustrative examples of suitable sulfonic acids includemahogany sulfonic acids, petrolatum sulfonic acids,monoeicosane-substituted naphthalene sulfonic acids, dodecylbenzenesulfonic acids, didodecylbenzene sulfonic acids, dinonylbenzene sulfonicacids, cetylchlorobenzene sulfonic acids, dilauryl beta-naphthalenesulfonic acids, the sulfonic acid derived by the treatment ofpolyisobutene having a molecular weight of 1500 with chlorosulfonicacid, nitronaphthalenesulfonic acid, paraffin wax sulfonic acid,cetyl-cyclopentane sulfonic acid, lauryl-cyclohexanesulfonic acids,polyethylene (M.W. 750) sulfonic acids, etc. Obviously, it is necessarythat the size and number of aliphatic groups on the aryl sulfonic acidsbe sufficient to render the acids soluble. Normally the aliphatic groupswill be alkyl and/or alkenyl groups such that the total number ofaliphatic carbons is at least twelve.

Within this preferred group of overbased carboxylic and sulfonic acids,the barium and calcium overbased mono-, di-, and tri-alkylated benzeneand naphthalene (including hydrogenated forms thereof), petrosulfonicacids, and higher fatty acids are especially preferred. Illustrative ofthe synthetically produced alkylated benzene and naphthalene sulfonicacids are those containing alkyl substituents having from 8 to about 30carbon atoms therein. Such acids include di-isododecyl-benzene sulfonicacid, wax-substituted phenol sulfonic acid, wax-substituted benzenesulfonic acids, polybutene-substituted sulfonic acid,cetyl-chlorobenzene sulfonic acid, di-cetylnaphthalene sulfonic acid,di-lauryldiphenylether sulfonic acid, diisononylbenzene sulfonic acid,di-isooctadecylbenzenesulfonic acid, stearylnaphthalene sulfonic acid,and the like. The petroleum sulfonic acids are a well known artrecognized class of materials which have been used as starting materialsin preparing overbased products since the inception of overbasin gtechniques as illustrated by the above patents. Petroleum sulfonic acidsare obtained by treating refined or semi-refined petroleum oils withconcentrated or fuming sulfuric acid. These acids remain in the oilafter the settling out of sludges. These petroleum sulfonic acids,depending on the nature of the petroleum oils from which they areprepared, are oil-soluble alkane sulfonic acids, alkyl-substitutedcycloaliphatic sulfonic acids including cycloalkyl sulfonic acids andcycloalkene sulfonic acids, and alkyl, alkaryl, or aralkyl substitutedhydrocarbon aromatic sulfonic acids including single and condensedaromatic nuclei as well as partially hydrogenated forms thereof.Examples of such pctrosulfonic acids include mahogany sulfonic acid,white oil sulfonic acid, petrolatum sulfonic acid, petroleum naphthenesulfonic acid, etc. This especially preferred group of aliphatic fattyacids includes the saturated and unsaturated higher fatty acidscontaining from 12 to about 30 carbon atoms. Illustrative of these acidsare lauric acid, palmitic acid, oleic acid, linoletic acid, linolenicacid, oleo-stearic acid, stearic acid, myristic acid, and undecalinicacid, alphachlorostearic acid, and alpha-nitrol-auric acid.

As shown by the representative examples of the preferred classes ofsulfonic and carboxylic acids, the acids may contain non-hydrocarbonsubstituents such as halo, nitro, alkoxy, hydroxyl, and the like.

It is desirable that the overbased materials used to prepare thedisperse system have a metal ratio of at least about 3.5 and preferablyabout 4.5. An especially suitable group of the preferred sulfonic acidoverbased materials has a metal ratio of at least about 7.0. Whileoverbased materials having a metal ratio of have been prepared, normallythe maximum metal ratio will not exceed about 30 and, in most cases, notmore than about 20.

The overbased materials used in preparing the colloidal disperse systemsutilized in the polymeric compositions of the invention contain fromabout 10% to about 70% by weight of metal-containing components. Asexplained hereafter, the exact nature of these metal containingcomponents is not known. It is theorized that the metal base, the acidicmaterial, and the organic material being overbased form a metal complex,this complex being the metal-containing component of the overbasedmaterial. On the other hand, it has also been postulated that the metalbase and the acidic material form amorphous metal compounds which aredissolved in the inert organic reaction medium and the material which issaid to be overbased. The material which is overbased may itself be ametal-containing compound, e.g., a carboxylic or sulfonic acid metalsalt. In such a case, the metal-containing components of the overbasedmaterial would be both the amorphous compounds and the acid salt. Theexact nature of these overbased materials is obviously not critical inthe present invention since these materials are used only asintermediates. The remainder of the overbased materials consistessentially of the inert organic reaction medium and any promoter whichis not removed from the overbased product. For purposes of thisapplication, the organic material which is subjected to overbasing isconsidered a part of the metal-containing components. Normally, theliquid reaction medium constitutes at least about 30% by weight of thereaction mixture utilized to prepare the overbased materials.

As mentioned above, the colloidal disperse systems used in thecomposition of the present invention are prepared by homogenizing aconversion agent and the overbased starting material. Homogeniz-ation isachieved by vigorous agitation of the two components, preferably at thereflux temperature or a temperature slightly below the refluxtemperature. The reflux temperature normally will depend upon theboiling point of the conversion agent. However, homogenization may beachieved Within the range of about 25 C. to about 200 C. or slightlyhigher. Usually, there is no real advantage in exceeding 150 C.

The concentration of the conversion agent necessary to achieveconversion of the overbased material is usually within the range of fromabout 1% to about based upon the weight of the overbased materialexcluding the weight of the inert, organic solvent and any promoterpresent therein. Preferably at least about 10% and usually less thanabout 60% by weight of the conversion agent is employed. Concentrationsbeyond 60% appear to afford no additional advantages.

The terminology conversion agent as used in the specification and claimsis intended to describe a class of very diverse materials which possessthe property of being able to convert the Newtonian homogeneous,singlephase, overbased materials into non-Newtonian colloidal dispersesystems. The mechanism by which conversion is accomplished is notcompletely understood. However, with the exception of carbon dioxide,these conversion agents all possess active hydrogens. The conversionagents include lower aliphatic carboxylic acids, water, aliphaticalcohols, cycloaliphatic alcohols, arylaliphatic alcohols, phenols,ketones, aldehydes, amines, boron acids, phosphorus acids, and carbondioxide. Mixtures of two or more of these conversion agents are alsouseful. Particularly useful conversion agents are discussed below.

The lower aliphatic carboxylic acids are those containing less thanabout eight carbon atoms in the molecule. Examples of this class ofacids are formic acid, acetic acid, propionic acid, butyric acid,valeric acid, isovaleric acid, isob-utyric acid, caprylic acid,heptanoic acid, chloroacetic acid, dichloroacetic acid, trichloroaceticacid, etc. Formic acid, acetic acid, and ropionic acid, are preferredwith acetic acid being especially suitable. It is to be understood thatthe anhydrides of these acids are also useful and, for the purposes ofthe specification and claims of this invention, the term acid isintended to include both the acid per se and the anhydride of the acid.

Useful alcohols include aliphatic, cycloaliphatic, and arylaliphaticmonoand polyhydroxy alcohols. Alcohols having less than about twelvecarbons are especially useful while the lower alkanols, i.e., alkanolshaving less than about eight carbon atoms are preferred for reasons ofeconomy and effectiveness in the process. Illustrative are the alkanolssuch as methanol, ethanol, isopropanol, n-propanol, isobutanol, tertiarybutanol, isooctatnol, dodecanol, n-pentanol, etc; cycloalkyl alcoholsexemplified by cyclopentathol, cyclohexanol, 4-methylcyclohexanol,2-cyclohexylethanol, cyclopentylmethanol, etc; phenyl aliphatic alkanolssuch as benzyl alcohol, Z-phenylethanol, and cinnamyl alcohol; alkyleneglycols of up to about six carbon atoms and mono-lower alkyl ethersthereof such as monomethylether of ethylene glycol, diethylene glycol,ethylene glycol, trimethylene glycol, hexamethylene glycol, triethyleneglycol, 1,4-butanediol, 1,4-cyclohexanediol, glycerol, andpentaerythritol.

The use of a mixture of water and one or more of the alcohols isespecially effective for converting the overbased material to colloidaldisperse systems. Such combinations often reduce the length of timerequired for the process. Any water-alcohol combination is effective buta very effective combination is a mixture of one or more alcohols andwater in a weight ratio of alcohol to water of from about 0.05:1 toabout 24:1. Preferably, at least one lower alkanol is present in thealcohol component of these water-alkanol mixtures. Water-alkanolmixtures wherein the alcoholic portion is one or more lower alkanols areespecially suitable. Alcoholzwater conversions are illustrated inco-pending application Ser. No. 535,693, filed Mar. 21, 1966.

Phenols suitable for use as conversion agents include phenol, naphthol,ortho-cresol, para-cresol, catechol, mixtures of cresol,para-tert-butylphenol, and other lower alkyl substituted phenols,meta-polyisobutene (M.W. 350)-substituted phenol, and the like.

Other useful conversion agents include lower aliphatic aldehydes andketones, particularly lower alkyl aldehydes and lower alkyl ketones suchas acetaldehydes, propionaldehydes, butyraldehydes, acetone, methylethylketone, diethyl ketone. Various aliphatic, cycloaliphatic, aromatic, andheterocyclic amines are also useful providing they contain at least oneamino group having at least one active hydrogen attached thereto.Illustrative of these amines are the monoand di-alkylamines, particularlmonoand di-lower alkylamines, such as methylamine, ethylamine,propylamine, dodecylamine, methyl ethylamine, diethylamine; thecycloalkylamines such as cyclohexylamine, cyclopentylamine, and thelower alkyl substituted cycloalkylamines such as3-methylcyclohexylamine; 1,4-cyclohexylenediamine; arlyamines such asaniline, mono-, di-, and tri-, lower alkyl-substituted phenyl amines,naphthylamines, 1,4-phenylene diamines; lower alkanol amines such asethanolamine and diethanolamine; alkylenediamines such as ethylenediamine, triethylene tetramine, propylene diamines, octamethylenediamines; and heterocyclic amines such as piperazine,4-aminoethylpiperazine, 2-octadecyl-imidazoline, and oxazolidine. Boronacids are also useful conversion agents and include boronic acids (e.g.,alkyl-B(OH) or aryl-B(OH boric acid (i.e., H BO tetraboric acid,metaboric acid, and esters of such boron acids.

The phosphorus acids are useful conversion agents and include thevarious alkyl and aryl phosphinic acids, phosphinus acids, phosphonicacids, and phosphonous acids. Phosphorus acids obtained by the reactionof lower alkanols or unsaturated hydrocarbons such as polyisobuteneswith phosphorus oxides and phosphorus sulfides are particularly useful,e.g., P 0 and P S Carbon dioxide can be used as the conversion agent.However, it is preferable to use this conversion agent in combinationwith one or more of the foregoing conversion agents. For example, thecombination of water and carbon dioxide is particularly effective as aconversion agent for transforming the overbased materials into acolloidal disperse system.

As previously mentioned, the overbased materials are single phasehomogeneous systems. However, depending on the reaction conditions andthe choice of reactants in preparing the overbased materials, theresometimes are present in the product insoluble contaminants. Thesecontaminants are normally unreacted basic materials such as calciumoxide, barium oxide, calcium hydroxide, barium hydroxide, or other metalbase materials used as a reactant in preparing the overbased material.It has been found that a more uniform colloidal disperse system resultsif such contaminants are removed prior to homogenizing the overbasedmaterial with the conversion agents. Obviously a more uniform dispersesystem makes it possible to achieve reproducibility of properties inresinous compositions containing such systems. Accordingly, it ispreferred that any insoluble contaminants in the overbased materials beremoved prior to converting the material in the colloidal dispersesystem. The removal of such contaminants is easily accomplished byconventional techniques such as filtration or centrifugation. It shouldbe understood however, that the removale of these contaminants, whiledesirable for reasons just mentioned, is not an absolute essentialaspect of the invention and useful products can be obtained whenoverbased materials containing insoluble contaminants are converted tothe colloidal disperse systems.

The conversion agents or a proportion thereof may be retained in thecolloidal disperse system. The conversion agents are however, notessential components of these disperse systems and it is usuallydesirable that as little of the conversion agents as possible beretained in the disperse systems. Since these conversion agents do notreact with the overbased material in such a manner as to be permanentlybound thereto through some type of chemical bonding, it is normally asimple matter to remove a major proportion of the conversion agents and,generally, substantially all of the conversion agents, Some of theconversion agents have physical properties which make them readilyremovable from the disperse systems. Thus, most of the free carbondioxide gradually escapes from the disperse system during thehomogenization process or upon standing thereafter. Since the liquidconversion agents are generally more volatile than the remainingcomponents of the disperse system, they are readily removable byconventional devolatilization techniques, e.g., heating, heating atreduced pressures, and the like. For this reason, it may be desirable toselect conversion agents which will have boiling points which are lowerthan the remaining components of the disperse system. This is anotherreason Why the lower alkanols, mixtures thereof, and lower alkanol-watermixtures are preferred conversion agents.

Again, it is not essential that all of the conversion agent be removedfrom the disperse systems. In fact, useful disperse systems foremployment in the resinous compositions of the invention result withoutremoval of the conversion agents. However, from the standpoint ofachieving uniform results, it is generally desirable to remove theconversion agents, particularly Where they are volatile. In some cases,the liquid conversion agents may facilitate the mixing of the colloidaldisperse system with the polymeric resin material. In such cases, it isadvantageous to permit the conversion agents to remain in the dispersesystem until it is mixed with the polymeric resin, Thereafter, theconversion agents can be removed from the mixture of the disperse systemand polymeric resins by conventional devolatilization techniques ifdesired.

To better illustrate the colloidal disperse systems utilized in theinvention, the procedure for preparing a preferred system is describedbelow:

THE OVERBASED MATERIAL As stated above, the essential materials forpreparing an overbased product are (1) the organic material to beoverbased, (2) an inert, non-polar organic solvent for the organicmaterial, (3) a metal base, (4) a promoter, and (5) an acidic material.In this example, these materials are (1) calcium petrosulfonate, (2)mineral oil, (3) calcium hydroxide, (4) a mixture of methanol,isobutanol, and n-pentanol, and (5 carbon dioxide.

A reaction mixture of 1305 grams of calcium sulfonate having a metalratio of 2.5 dissolved in mineral oil, 220 grams of methyl alcohol, 72grams of isobutanol, and 38 grams of n-phentanol is heated to 35 C. andsubjected to the following operating cycle four times: mixing with 143grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 3239. The resulting product isthen heated to 155 C. during a period of 9 hours to remove the alcoholsand then filtered at this temperature. The filtrate is a calciumoverbased petrosulfonate having a metal ratio of 12.2.

CONVERSION TO A COLLOIDAL DISPERSE SYSTEM A mixture of 150 parts of theoverbased material, parts of methyl alcohol, 10.5 parts of n-pentanoland 45 parts of water is heated under reflux conditions at 71"- 74 C.for 13 hours. The mixture becomes a gel. It is then heated to 144" overa period of 6 hours and diluted with 126 parts of mineral oil having aviscosity of 2000 SUS at 100 F. and the resulting mixture heated at 144C. for an additional 4.5 hours with stirring. This thickened product isa colloidal disperse system of the type contemplated by the presentinvention.

The disperse systems of the invention are characterized by threeessential components: (A) solid, metal-containing particles formed insitu, (B) an inert, non-polar, organic liquid which functions as thedisperse medium, and (C) an organic compound which is soluble in thedisperse medium and the molecules of which are characterized by ahydrophobic portion and at least one polar substituent. In the colloidaldisperse system described immediately above, these components are asfollows: (A) calcium carbonate in the form of solid particles, (B)mineral oil, and (C) calcium petrosulfonate.

From the foregoing example, it is apparent that the solvent for thematerial which is overbased becomes the colloidal disperse medium or acomponent thereof, Of course, mixt r s of other inert liquids can besubstituted for the mineral oil or used in conjunction with the mineraloil prior to forming the overbased material. Moreover, after theoverbased material is prepared, additional liquid material, e.g., aplasticizer for the resin can be added if desired, to form a part of thedisperse medium.

It is also readily seen that the solid, metal-containing particlesformed in situ possess the same chemical composition as would thereaction products of the metal base and the acidic material used inpreparing the overbased materials. Thus, the actual chemical identity ofthe metal containing particles formed in situ depends upon both theparticular metal base or, bases employed and the particular acidicmaterial or materials reacted therewith. For example, if the metal baseused in preparing the overbased material were barium oxide and if theacidic material was a mixture of formic and acetic acids, themetalcontaining particles formed in situ would be barium formates andbarium acetates.

However, the physical characteristics of the particles formed in situ inthe conversion step are quite different from the physicalcharacteristics of any particles present in the homogeneous,single-phase overbased material which is subjected to the conversion.Particularly, such physical characteristics as particle size andstructure are quite different. The solid, metal-containing particles ofthe colloidal disperse systems are of a size sufficient for detection byX-ray ditfraction. The overbased material prior to conversion are notcharacterized by the presence of these detectable particles.

X-ray diffraction and electron microscope studies have been made of bothoverbased organic materials and col loidal disperse systems preparedtherefrom. These studies establish the presence in the disperse systemsof the solid, metal-containing salts. For example, in the dispersesystem prepared herein above, the calcium carbonate is present as solidcalcium carbonate having a particle size of about 40 to 50 A. (unitparticle size) and interplanar spacing (dA.) of 3.035. But X'raydiffraction studies of the overbased material from which it was preparedindicate the absence of calcium carbonate of this type. In fact, calciumcarbonate present as such, if any, appears to be amorphous and insolution. While applicant does not intend to be bound by any theoryoffered to explain the changes which accompany the conversion step, itappears that conversion permits particle formation and growth. That is,the amorphous, metal-containing apparently dissolved salts or complexespresent in the overbased material form solid, metal-contatiningparticles which by a process of particle growth become colloidalparticles. Thus, in the above example, the dissolved amorphous calciumcarbonate salt or complex is transformed into solid particles which thengrow. In this examp e, they grow to a size of 40 to 50 A. In many cases,these particles apparently are crystallites. Regardless of the corectness of the postulated mechanism for in situ particle formation thefact remains that no particles of the type predominant in the dispersesystems are found in the overbased materials from which they areprepared. Accordingly, they are unquestionably formed in situ duringconversion.

As these solid metal-containing particles formed in situ come intoexistence, they do so as pre-wet, predispersed solid particles which areinherently uniformly distributed throughout the other components of thedisperse system. The liquid disperse medium containing these pre-wetdispersed particles is readily incorporated into various polymericcompositions thus facilitating the uniform distribution of the particlesthroughout the polymeric resin composition. This pre-wet, pre-dispersedcharacter of the solid metal-containing particles resulting from theirin situ formation is, thus, an extremely important feature of thedisperse systems.

In the foregoing example, the third component of the disperse system(i.e., the organic compound which is soluble in the disperse medium andwhich is characterized by molecules having a hydrophobic portion and apolar substituent) is calcium petrosulfonate,

wherein R is the residue of the petrosulfonic acid. In this case, thehydrophobic portion of the molecule is the hydrocarbon moiety ofpetrolsulfonic, i.e., -R The polar substituent is the metal salt moiety,

it i SO-CaO-S II II The hydrophobic portion of the organic compound is ahydrocarbon radical or a substantially hydrocarbon radical containing atleast about twelve aliphatic carbon atoms. Usually the hydrocarbonportion is an aliphatic or cycloaliphatic hydrocarbon radical althoughaliphat1c or cycloaliphatic substituted aromatic hydrocarbon radicalsare also suitable. In other words, the hydrophobic portion of theorganic compound is the residue of the organic material which isoverbased minus its polar substituents. For example, if the material tobe overbased is a carboxylic acid, sulfonic acid, or phosphorus acid,the hydrophobic portion is the residue of these acids which would resultfrom the removal of the acid functions. Similarly, if the material to beoverbased is a phenol, a nitro-substituted polyolefin, or an amine, thehydrophobic portion of the organic compound is the radical resultingfrom the removal of the hydroxyl, nitro, or amino group respectively. Itis the hydrophobic portion of the molecule which renders the organiccompound soluble in the solvent used in the overbasing process and laterin the disperse medium.

Obviously, the polar portion of these organic compounds are the polarsubstituents such as the acid salt moiety discussed above. When thematerial to be overbased contains polar substituents which will reactwith the basic metal compound used in overbasing, for example, acidgroups such as carboxy, sulfino, hydroxysulfonyl, and phosphorus acidgroups or hydroxyl groups, the polar substituent of the third componentis the polar group formed from the reaction. Thus, the polar substituentis the corresponding acid metal salt group or hydroxyl group metalderivative, e.g., an alkali or alkaline earth metal sulfonate,carboxylate, sulfinate, alcoholate, or phenate.

On the other hand, some of the materials to be overbased contained polarsubstituents which ordinarily do not react with metal bases. Thesesubstituents include nitro, amino, ketocarboxyl, carboalkoxy, etc. Inthe disperse systems derived from overbased materials of this type thepolar substituents in the third component are unchanged from theiridentity in the material which was originally overbased.

The identity of the third essential component of the disperse systemdepends upon the identity of the starting materials (i.e., the materialto be overbased and the metal base compound) used in preparing theoverbased material. Once the identity of these starting materials isknown, the identity of the third component in the colloidal dis persesystem is automatically established. Thus, from the identity of theoriginal material, the identity of the hydrophobic portion of the thirdcomponent in the disperse system is readily established as being theresidue of that material minus the polar substituents attached thereto.The identity of the polar substituents on the third component isestablished as a matter of chemistry. If the polar groups on thematerial to be overbased undergo reaction with the metal base, forexample, if they are acid functions, hydroxy groups, etc., the polarsubstituent in the final product will correspond to the reaction productof the original substituent and the metal base. On the other hand, ifthe polar substituent in the material to be overbased is one which doesnot react with metal bases,

then the polar substituent of the third component is the same as theoriginal substituent.

As previously mentioned, this third component can orient itself aroundthe metal-containing particles to form micellar colloidal particles.Accordingly, it can exist in the disperse system as an individual liquidcomponent dissolved in the disperse medium or it can be associated withthe metal-containing particles as a component of micellar colloidalparticles.

PREPARATION OF THE RESINOUS COMPOSITIONS The specific means by which agiven disperse system is incorporated into a particular resinouscomposition does not constitute a critical feature of the presentinvention. Those skilled in the art constantly prepare resinouscompositions cotntaining an extremely diverse group of additives, bothsolid and liquid, through a variety of knowntechniques. Fillers,pigments, stabilizers, plasticizers, thixotropic agents, etc., areroutinely made a part of polymeric resinous compositions. Therefore, avariety of suitable methods for incorporating the disperse systems intoresinous compositions are obvious to those skilled in the art. Forexample, as the colloidal disperse systems of the invention are liquidsor semi-liquids (i.e., gels) they can be mixed directly with a plastisolor organisol prior to curing. Or the disperse systems can be premixedwith all or part of any other liquid additive or component (e.g.,plasticizers, solvents, stabilizers, etc.) used in the resinouscompositions and this resulting mixture incorporated into the polymericcomposition. In other words, these disperse systems are mixed with theremaining components of a polymeric composition in the same manner asany other thixotropic agent or additive. Illustrative techniques forincorporating the disperse systems into polymeric materials areillustrated in the examples presented hereinafter.

The disperse systems are added to the resinous composition in an amountof from about 0.1% to about 25% by Weight based on the weight of polymerpresent in the composition. Preferably, from about 2% to about 15% willbe used. Particularly useful compositions contain from about 4% to about8% of the disperse systems. The optimum amount for any given compositiondepends upon the particular resin or combination of resins contained inthe composition, the amount and type of the other components present,the particular use to which the composition is to be used, and theparticular disperse system. However, using the above concentrations asguidelines, it is well within the skill of the art to determine theoptimum amount of a given disperse system for a particular resinouscomposition having a particular use.

The following examples illustrate various overbased materials, colloidaldisperse systems prepared from these overbased materials, and resinouscompositions contain ing various colloidal disperse systems. Unlessotherwise indicated, percentages and parts refer to percent by Weightand parts by weight. Where temperatures exceed the boiling points of thecomponents of the reaction mixture, obviously reflux conditions areemployed unless the reaction products are being heated to removevolatile components.

Examples 1 through 43 are directed to the preparation of overbasedmaterials illustrative of the types which can be used to prepare thenon-Newtonian colloidal disperse systems used in the polymeric resinouscompositions of the invention. The term naphtha as used in the followingexamples refers to petroleum distillates boiling in the range of aboutC. to about C. and usually designated Varnish Makers and PaintersNaphtha.

Example 1 To a mixture of 3,245 grams (12.5 equivalents) of a mineraloil solution of barium petroleum sulfonate (sulfate ash of 7.6%), 32.5parts of octylphenol, 197 parts 19 of water, there is added 73 parts ofbarium oxide within a period of 30 minutes at 5784 C. The mixture isheated at 100 C. for 1 hour to remove substantially all water and blownwith 75 parts of carbon dioxide at 133 to 170 C. within a period of 3hours. A mixture of 1,000 grams of the above carbonated intermediateproduct, 121.8 parts of octylphenol, and 234 parts of barium hydroxideis heated at 100 C. and then at 150 C. for 1 hour. The mixture is thenblown with carbon dioxide at 150 C. for 1 hour at a rate of 3 cubic feetper hour. The carbonated product is filtered and the filtrate is foundto have a sulfate ash content of 39.8% and a metal ratio of 9.3.

Example 2 To a mixture of 3,245 grams (12.5 equivalents) of bariumpetroleum sulfonate, 1,460 grams (7.5 equivalents) of heptylphenol, and2,100 grams of water in 8,045 grams of mineral oil there is added at 180C. 7,400 grams (96.5 equivalents) of barium oxide. The addition ofbarium oxide causes the temperature to rise to 143 C. which temperatureis maintained until all the water has been distilled. The mixture isthen blown with carbon dioxide until it is substantially neutral. Theprod not is diluted with 5,695 grams of mineral oil and filtered. Thefiltrate is found to have a barium sulfate ash content of 30.5% and ametal ratio of 8.1. Another inert liquid such as benzene, toluene,heptene, etc., can be substituted for all or part of the mineral oil.

Example 3 A mixture of 1,285 grams (1.0 equivalent) of 40% bariumpetroleum sulfonate and 500 milliliters (12.5 equivalents) of methanolis stirred at 5560 C. while 301 grams (3.9 equivalents) of barium oxideis added portionwise over a period of 1 hour. The mixture is stirred anadditional 2 hours at 45-55 C., then treated with carbon dioxide at55-65 C. for 2 hours. The resulting mixture is freed of methanol byheating to 150 C. The residue is filtered through a siliceous filteraid, the clear, brown filtrate analyzing as: sulfate ash, 33.2%;slightly acid; metal ratio, 4.7.

Example 4 A stirred mixture of 57 grams (0.4 equivalents) of nonylalcohol and 3.01 grams (3.9 equivalents) of barium oxide is heated at150175 C. for an hour, then cooled to 80 C. whereupon 400 grams (12.5equivalents) of methanol is added. The resultant mixture is stirred at7075 C. for 30 minutes, then treated with 1,285 grams (1.0 equivalent)of 40% barium petroleum sulfonate. This mixture is stirred at refluxtemperature for an hour, then treated with carbon dioxide at 6070 C. for2 hours. The mixture is then heated to 160 C. at a pressure of 18millimeters of mercury and thereafter filtered. The filtrate is a clear,brown oily material having the following analysis: sulfate ash, 32.5%;neutralization number nil; metal ratio, 4.7.

Example 5 (a) To a mixture of 1,145 grams of a mineral oil solution of a40% solution of barium mahogany sulfonates (1.0 equivalent) and 100grams of methyl alcohol at 55 C., there is added 220 grams of bariumoxide while the mixture is being blown with carbon dioxide at a rate of2 to 3 cubic feet per hour. To this mixture there is added an additional78 grams of methyl alcohol and then 460 grams of barium oxide while themixture is blown with carbon dioxide. The carbonated product is heatedto 150 C. for 1 hour and filtered. The filtrate is found to have abarium sulfate ash content of 53.8% and a metal ratio of 8.9.

(b) A carbonated basic metal salt is prepared in accordance with theprocedure of (a) except that a total of 16 equivalents of barium oxideis used per equivalent of the barium mahogany sulfonate. The productpossesses a metal ratio of 13.4.

Example 6 A mixture of 520 parts (by weight) of a mineral oil, 480 partsof a sodium petroleum sulfonate (molecular weight of 480), and 84 partsof Water is heated at 100 C. for 4 hours. The mixture is then heatedwith 86 parts of a 76% aqueous solution of calcium chloride and 72 partsof lime (90% purity) at C. for 2 hours, dehydrated by heating to a watercontent of less than 0.5% cooled to 50 C., mixed with parts of methylalcohol, and then blown with carbon dioxide at 50 C. until substantiallyneutral. The mixture is then heated to C. to remove the methyl alcoholand water and the resulting oil solution of the basic calcium sulfonatefiltered. The filtrate is found to have a calcium sulfate ash content of16% and a metal ratio of 2.5.

A mixture of 1,305 grams of the above carbonated cal cium sulfonate, 930grams of mineral oil, 220 grams of methyl alcohol, 72 grams of isobutylalcohol, and 38 grams of primary amyl alcohol is prepared, heated to 35C., and subjected to the following operating cycle 4 times: mixing with143 grams of 90% calcium hydroxide and treating the mixture with carbondioxide until it has a base number of 3239. The resulting prodnet isthen heated to C. during a period of 9 hours to remove the alcohols andfiltered through a siliceous filter aid at this temperature. Thefiltrate has a calcium sulfate ash content of 39.5% and a metal ratio of12.2.

Example 7 A basic metal salt is prepared by the procedure described inExample 6 except that the slightly basic calcium sulfonate having ametal ratio of 2.5 is replaced with a mixture of that calcium sulfonate(280 parts by Weight) and tall oil acid (970 parts by Weight having anequivalent weight of 340) and that the total amount of calcium hydroxideused is 930 parts by weight. The resulting highly basic metal salt ofthe process has .21 calcium sulfate ash content of 48%, a metal ratio of7.7, and an oil content of 31%.

Example 8 A highly basic metal salt is prepared by the procedure ofExample 7 except that the slightly basic calcium sulfonate startingmaterial having a metal ratio of 2.5 is replaced with tall oil acids(1,250 parts by weight, having an equivalent weight of 340) and thetotal amount of calcium hydroxide used is 772 parts by weight. Theresulting highly basic metal salt has a metal ratio of 5.2, a calciumsulfate ash content of 41%, and an oil content of 33%.

Example 9 A normal calcium mahogany sulfonate is prepared by metathesisof a 60% oil solution of sodium mahogany sulfonate (750 parts by weight)with a solution of 67 parts of calcium chloride and 63 parts of water.The reaction mass is heated for 4 hours at 90 to 100 C. to effect theconversion of the sodium mahogany sulfonate to calcium mahoganysulfonate. Then 54 parts of lime is added and the Whole is heated to 150C. over a period of 5 hours. When the whole has cooled to 40 C., 98parts of methanol is added and 152 parts of carbon dioxide is introducedover a period of 20 hours at 4243 C. Water and alcohol are then removedby heating the mass to 150 C. The residue in the reaction vessel isdiluted with 100 parts of low viscosity mineral oil. The filtered oilsolution of the desired carbonated calcium sulfonate overbased materialshows the following analysis: sulfate ash content, 16.4%; neutralizationnumber, 0.6 (acidic); and a metal ratio of 2.50. By adding barium orcalcium oxide or hydroxide to this product with subsequent carbonation,the metal ratio can be increased to a ratio of 3.5 or greater asdesired.

A mixture of 880 grams (0.968 moles) of a 57.5% oil solution of thecalcium sulfonate of tridecylbenzene bottoms (the bottoms constitute amixture of mono-, di-, and tri-decylbenzene), 149 grams of methanol, and59 grams (1.58 equivalents) of calcium hydroxide are introduced into areaction vessel and stirred vigorously. The whole is heated to 40-45 C.and carbon dioxide is introduced for 0.5 hours at the rate of 2 cubicfeet per hour. The carbonated recation mixture is then heated to 150 C.to remove alcohol and any water present, and the residue is filtered forpurposes of purification. The product, a 61% oil solution of the desiredoverbased carbonated calcium sulfonate material shows the followinganalysis: ash content, 16.8%; neutralization number, 7.0 (acidic); andmetal ratio, 2.42. By further carbonation in the presence of an alkalior alkaline earth metal oxide, hydroxide, or alkoxide, the metal ratiocan readily be increased to 3.5 or greater.

Example 11 A mixture of 2,090 grams (2.0 equivalents) of a 45% oilsolution of calcium mahogany sulfonate containing 1% of water, 74 grams(2.0 equivalents) of calcium hydroxide, and 251 grams of ethylene glycolis heated for 1 hour at 100 C. Carbon dioxide is then bubbled throughthe mixture at 40-45 C. for 5.5 hours. The ethylene glycol and any waterpresent are removed by heating the mixture to a temperature of 185 C. at10.2 millimeters of mercury. The residue is filtered yielding thedesired overbased calcium sulfonate material, having the followinganalysis: sulfate ash, 12.9%; neutralization number 5.0 (acidic); and ametal ratio of 2.0 which can be increased to 3.5 or greater as desiredby carbonation in the presence of calcium oxide or hydroxide.

Example 12 A mixture comprising 1,595 parts of the overbased material ofExample 9 (1.54 equivalents based on sulfonic acid anion), 167 parts ofthe calcium phenate prepared as indicated below (0.19 equivalent), 616parts of mineral oil, 157 parts of 91% calcium hydroxide (3.86equivalents), 288 parts of methanol, 88 parts of isobutanol, and 56parts of mixed isomeric primaryamyl alcohols (containing about 65%normal amyl, 3% isoamyl and 32% of 2-methyl-1-butyl alcohols) is stirredvigorously at 40 C. and 25 parts of carbon dioxide is introduced over aperiod of 2 hours at 4050 C. Thereafter, three additional portions ofcalcium hydroxide, each amounting to 1.57 parts, are added and each suchaddition is followed by the introduction of carbon dioxide as previouslyillustrated. After the fourth calcium hydroxide addition and thecarbonation step is completed, the reaction mass is carbonated for anadditional hour at 4347 C. to reduce neutralization number of the massto 4.0 (basic). The substantially neutral, carbonated reaction mixtureis freed from alcohol and any Water of reaction by heating to 150 C. andsimultaneously blowing it with nitrogen. The residue in the reactionvessel is filtered. The filtrate, an oil solution of the desiredsubstantially neutral, carbonated calcium sulfonate overbased materialof high metal ratio, shows the following analysis: sulfate ash content,41.11%; neutralization number 0.9 (basic); and a metal ratio of 12.55.

The calcium phenate used above is prepared by adding 2,250 parts ofmineral oil, 960 parts (5 moles) of heptylphenol, and 50 parts of waterinto a reaction vessel and stirring at 25 C. The mixture is heated to 40C. and 7 parts of calcium hydroxide and 231 parts (7 moles) of 91%commercial paraformaldehyde is added over a period of 1 hour. The Wholeis heated to 80 C. and 200 additional parts of calcium hydroxide (makinga total of 207 parts or 5 moles) is added over a period of 1 hour at8090 C. The whole is heated to 150 C. and maintained at that temperaturefor 12 hours while nitrogen is blown through the mixture to assist inthe removal of water. If foaming is encountered, a few drops ofpolymerized dimethyl silicone foam inhibitor may be added to control thefoaming. The reaction mass is then filtered. The filtrate, a 33.6% oilsolution of the desired calcium phenate of heptylphenol-formaldehydecondensation product is found to contain 7.56% sulfate ash.

Example 13 A mixture of 574 grams (0.5 equivalents) of 40% bariumpetroleum sulfonate, 98 grams (1.0 equivalents) of furfuryl alcohol, and762 grams of mineral oil is heated with stirring at 100 C. for an hour,then treated portionwise over a 15-minute period with 230 grams (3.0equivalents) of barium oxide. During this latter period, the temperaturerises to C. (because of the exothermic nature of the reaction of bariumoxide and the alcohol). The mixture then is heated to 160 C. for anhour, and treated subsequently at this temperature for 1.5 hours withcarbon dioxide. The material is concentrated by heating to a temperatureof 150 C. at a pressure of 10 millimeters of mercury and thereafterfiltered to yield a clear, oil-soluble filtrate having the fol lowinganalysis: sulfate ash content, 21.4%; neutralization number, 2.6(basic); and a metal ratio of 6.1.

Example 14 An overbased material is prepared by the procedure of Example6 except that the slightly basic calcium sulfonate starting material hasa metal ratio of 1.6 and the amount of this calcium sulfonate used is10.50 parts (by Weight) and that the total amount of lime used is 630parts. The resulting metal salt has a calcium sulfate ash content of40%, a ratio of the inorganic metal group to the bivalent bridging groupof 16, and an oil content of 35%.

Example 15 To a mixture of 1614 parts (3 equivalents) of apolyisobutenyl succinic anhydride (prepared by the reaction of achlorinated polyisobutene having an average chlorine content of 4.3% andan average of 67 carbon atoms with maleic anhydride at about 200 C.),4313 parts of mineral oil, 345 parts (1.8 equivalents) of heptylphenol,and 200 parts of water, at 80 C., there is added 1,038 parts (24.7equivalents) of lithium hydroxide monohydrate over a period of 0.75hours while heating to 105 C. Isooctanol (75 parts) is added while themixture is heated to 150 C. over a 1.5-hour period. The mixture ismaintained at 150170 C. and blown with carbon dioxide at rate of 4 cubicfeet per hour for 3.5 hours. The reaction mixture is filtered through afilter aid and the filtrate is the desired product having a sulfate ashcontent of 18.9% and a metal ratio of 8.0.

Example 16 The procedure of Example 6 is repeated except that anequivalent amount of sodium hydroxide is used in lieu of the calciumoxide. The product is the corresponding sodium overbased material.

Example 17 A mixture of 244 parts (0.87 equivalent) of oleic acid, 180parts of primary isooctanol, and 400 parts of mineral oil is heated to70 C. whereupon 172.6 parts (2.7 equivalents) of cadmium oxide is added.The mixture is heated for 3 hours at a temperature of 150 to C. whileremoving water. Barium hydroxide monohydrate (324 parts, 3.39equivalents) is then added to the mixture over a period of 1 hour whilecontinuing to remove water by means of a side-arm water trap. Carbondioxide is blown through the mixture at a temperature of from 150160 C.until the mixture is slightly acidic to phenolphthalein. Upon completionof the carbonation, the mixture is stripped to a temperature of 150 C.at 35 mm. of mercury to remove substantially all the remaining water andalcohol. The

residue is the desired overbased product containing both barium andcadmium metal.

Example 18 The procedure of Example 13 is repeated except that thebarium sulfonate is replaced by an equivalent amount of potassiumsulfonate, and potassium oxide is used in lieu of the barium oxideresulting in the preparation of the corresponding potassium overbasedmaterial.

Example 19 A sulfoxide is prepared by treating polyisobutylene (averagemolecular weight 750) with 47.5% of its weight of SOC1 for 4.5 hours at220 C. A mixture of 787 grams (1.0 equivalent) of this sulfoxide, 124grams (0.6 equivalent) of diisobutylphenol, 550 grams of mineral oil,and 200 grams of water was warmed to 70 C. and treated with 360 grams(4.0 equivalents) of barium oxide. This mixture is heated at refluxtemperature for 1 hour and treated at 150 C. with carbon dioxide untilthe mixture is substantially neutral and thereafter filtered to yield aclear, oil-soluble liquid having the following analysis: sulfate ash,22.8%; neutralization number, 58 (basic); and metal ratio, 5.8.

Example 20 To a mixture of 268 grams (1.0 equivalent) of oleyl alcohol,675 grams of mineral oil, 124 grams (0.6 equivalent) ofdiisobutylphenol, and 146 grams of water, at 70 C. there is added 308grams (4.0 equivalents) of barium oxide. This mixture is heated atreflux temperature for 1 hour, then at 150 C. while bubbling carbondioxide therethrough until substantial neutrality of the mixture isachieved. The resulting reaction mass is filtered resulting in a clear,brown, oil-soluble filtrate having the following analysis: sulfate ashcontent, 29.8%; neutralization number 2.6 (basic); and metal ratio, 6.0.

Example 21 To a mixture of 423 grams (1.0 equivalent) of sperm oil, 124grams (0.6 equivalent) of heptylphenol, 500 grams of mineral oil, and150 grams of water there are added at 70 C. 308 grams (4.0 equivalents)of barium oxide. This mixture is heated at reflux temperature for 1hour, dried by heating at about 150 C. and thereafter carbonated bytreatment with carbon dioxide at the same temperature until the reactionmass was slightly acidic. Filtration yields a clear, light brown,non-viscous overbased liquid material having the following analysis:sulfate ash content, 32.0%; neutralization number (basic); metal ratio,6.5.

Example 22 To a mixture of 174 grams (1.0 equivalent) of N-octadecylpropylene diamine, 124 grams (0.6 equivalent) of diisobutylphenol, 766grams of mineral oil, 146 grams of water, there are added 306 grams (4.0equivalents) of barium oxide and the whole is refluxed for an hour.Water is subsequently removed by raising the temperature to 150 C. andthereafter carbon dioxide is bubbled therethrough While maintaining thistemperature. When the reaction mass is substantially neutral, carbondioxide addition is ceased and the reaction mass filtered producing aclear, oil-soluble liquid having the following analysis: sulfate ashcontent, 28.9%; neutralization number, 2.5 (basic); metal ratio, 5.8.

Example 23 A mixture of 6000 grams of a 30% solution of barium petroleumsulfonate (sulfate ash 7.6%), 348 grams of paratertiary butylphenol, and2911 grams of water are heated to a temperature 60 C. while slowlyadding 1100 grams of barium oxide and raising the temperature to 94 98C. The temperature is held within this range for about 1 hour and thenslowly raised over a period of 7%. hours to 150 C. and held at thislevel for an additional hour assuring substantial removal of all water.The resulting overbased material is a brown liquid having the followinganalysis: Sulfate ash content, 26.0%; metal ratio, 4.35.

This product is then treated with S0 until 327 grams of the masscombined with the overbased material. The product thus obtained has aneutralization number of Zero. The SO -treated material was liquid andbrown in color.

One thousand grams of the SO -treated overbased material producedaccording to the preceding paragraph is mixed with 286 grams of waterand heated to a temperature of about 60 C. Subsequently, 107.5 grams ofbarium oxide are added slowly and the temperature is maintained at 9498C. for 1 hour. Then the total reaction mass is heated to 150 C. over a 1hour period and held there for a period of 1 hour. The resultingoverbased material is purified by filtration, the filtrate being thebrown, liquid overbased material having the following analysis: sulfateash content, 33.7%; basic number, 38.6; metal ratio, 6.3.

Example 24 (a) A polyisobutylene having a molecular weight of 700-800 isprepared by the aluminum chloride-catalyzed polymerization ofisobutylene at 030 C., is nitrated with a 10% excess (1.1 moles) ofaqueous nitric acid at 70-75 C. for 4 hours. The volatile components ofthe product mixture are removed by heating to C. at a pressure of 75 mm.of mercury. To a mixture of 151 grams (0.19 equivalent) of this nitratedpolyisobutylene, 113 grams (0.6 equivalent) of heptylphenol, 155 gramsof water, and 2,057 grams of mineral oil there is added at 70 C. 612grams (8 equivalents) of barium oxide. This mixture is heated at 150 C.for an hour, then treated with carbon dioxide at this same temperatureuntil the mixture is neutral (phenolphthalein indicator; ASTM D 974-53Tprocedure at 25 C.; a measurement of the degree of conversion of themetal reactant, i.e., barium oxide, bicarbonation). The product mixtureis filtered and filtrate found to have the following analysis: sulfateash content, 27.6%; percent N, 0.06; and metal ratio, 9.

(b) A mixture of 611 grams (0.75 mole) of the nitrated polyisobutyleneof Example 1, 96 grams (0.045 mole) of heptylphenol, 2104 grams ofmineral oil, 188 grams of water and 736 grams (4.8 moles) of bariumoxide was heated at reflux temperature for an hour. The water wasvaporized and carbon dioxide passed into the mixture at 150 C. until themixture was no longer basic. This carbonated mixture was filtered andthe clear fluid filtrate showed the following analysis: sulfate ashcontent, 26.3%; percent N, 0.15; base No. 2.4; metal ratio, 6.7.

Example 25 (a) A mixture of 1 equivalent of a nitrated polypropylenehaving a molecular weight of about 3000, 2 equivalents of cetylphenol,mineral oil, and 3 equivalents of barium hydroxide is heated at refluxtemperature for 1 hour. The temperature is then raised to 150 C. andcarbon dioxide is bubbled through the mixture at this temperature. Thereaction product is filtered and the filtrate is the desired overbasedmaterial.

(b) A solvent-refined, acid-treated Pennsylvania petroleum lubricatingoil is nitrated by treatment with 1.5 moles of 70% aqueous nitric acidat 5478 C. for 8 hours. After removal of volatile components of theproduct mixture by heating at 103 C. at a pressure of 15 mm. of mercuryfor 2 hours, a 787 grams portion (1.0 equivalent) of the nitratedproduct is treated with 2 grams (0.3 equivalent) of heptylphenol, 495grams of mineral oil, grams of Water, and 378 grams (5 equivalents) ofbarium oxide. This mixture is heated at reflux temperature for an hour,then freed of water by distillation. The temperature is increased to C.whereupon carbon dioxide is bubbled into the mixture until it isneutral. Filtration yields a clear filtrate with the following analysis:percent sulfate ash, 27.6; percent N, 0.5 and metal ratio, 3.1.

Example 26 (a) A mixture of 1000 parts of mineral oil, 2 equivalents ofbarium hydroxide, 1 equivalent of 1-nitro-3- octadecyl-cyclohexane and 1equivalent (i.e., 0.5 mole) of 4,4'-methylene-bis(heptylphenol) iscarbonated at 100- 150 C. for 4 hours until the reaction mixture issubstantially neutral to phenolphthalein indicator. The reaction mass isfiltered and the desired product is the filtrate.

(b) A mixture of 1000 parts of mineral oil, 3- equivalents of lithiumhydroxide, 1 equivalent of nitrated polyisobutene (prepared by mixing500 parts by weight of polyisobutene having an average molecular weightof 1000 and 62.5 parts of 67% aqueous nitric acid at 6570 C. for 11hours) and para-butylphenol (1 equivalent) is carbonated according tothe technique of (a) above to produce the corresponding lithiumoverbased material.

Example 27 A coplymer of isobutene and piperylene (weight ratio of 98.2)having a molecular weight of about 2000, is nitrated by the procedureused in the preceding example for the nitration of polyisobutene. Anoverbased product is then prepared from this nitrated reactant by mixing1 equivalent thereof with 1 equivalent of a-butyl-B-naphthol and 7equivalents barium hydroxide, diluting the mixture with mineral oil to a50% oil mixture, and then carbonating the mixture at 120160 C. until itis substantially neutral to phenolphthalein indicator. The reactionproduct is filtered and the filtrate is the desired overbased product.

Example 28 A mixture of 630 grams (2 equivalents) of a rosin amine(consisting essentially of dehydroabietyl amine) having a nitrogencontent of 44% and 245 grams (1.2 equivalents) of heptylphenol having ahydroxyl content of 8.3% is heated to 90 C. and thereafter mixed with230 grams (3 equivalents) of barium oxide at 90140 C. The mixture ispurged with nitrogen at 140 C. A 600 gram portion is diluted with 400grams of mineral oil and filtered. The filtrate is blown with carbondioxide, diluted with benzene, heated to remove the benzene, mixed withxylene, and filtered. The filtrate, a 20% xylene solution of the producthas a barium sulfate ash content of 25.1%, a nitrogen content of 2%, anda reflux base number of 119. (The basicity of the metal composition isexpressed in terms of milligrams of KOH which are equivalent to one gramof the composition.) For convenience, the basicity thus determined isreferred to in the specification as a reflux base number.

Example 29 An amine-aldehyde condensation product is obtained asfollows: formaldehyde (420 grams, 14 moles) is added in small incrementsto a mixture comprising N- octadecylpropylenediamine (1,392 grams, 4moles), min, eral oil (300 grams), water (200 grams), and calciumhydroxide (42 gramscondensation catalyst) at the reflux temperature,i.e., 100-105 C. The rate of addition of formaldehyde is such as toavoid excessive foaming. The mixture is heated at reflux temperature for1 hour, slowly heated to 155 C., and blown with nitrogen at 150155 C.for 2 hours to remove all volatile components. It is then filtered. Thefiltrate, 93% of the theoretical yield, is a 65.4% oil solution of theamine-alde hyde condensation product having a nitrogen content of 2.4%.

A 1,850 gram portion (3.2 equivalents of nitrogen) is mixed with 1,850grams of heptylphenol (0.97 equivalents), 1,485 grams of mineral oil,and 1,060 grams of 90% pure barium oxide (12.6 equivalents) and heatedto 70 C. Over a period of 1 hour, 500 grams of water is added whilemaintaining the temperature in the range of 70-100 C. The mixture isheated at 110 to 115 C. for 4.7 hours and thereafter to 150 C. Whilemaintaining the temperature within the range of 140150 C the reactionmixture is carbonated and subsequently filtered. The filtrate is a 57.8%oil solution of the overbased amine-aldehyde condensation product havinga nitrogen content of 0.87% and a barium sulfate ash content of 29.5%.

Example 30 A partially acylated polyamine reactant is prepared asfollows: a mixture (565 parts by weight) of an alkylene amine mixtureconsisting of triethylene tetramine and diethylene triamine in weightratio of 3:1 is added at 2080 C. to a mixture of napthenic acid havingan acid number of 180 (1,270 parts) and oleic acid (1,110 parts). Thetotal quantity of the two acids used is such as to provide 1 equivalentof acid for each two equivalents of the amine mixture used. The reactionis exothermic. The mixture is blown with nitrogen while it is beingheated to 240 C. in 4.5 hours and thereafter heated at this temperaturefor 2 hours. Water is collected as the distillate.

To the above residue, ethylene oxide (140 parts) is added at 170-180 C.Within a period of 2 hours While nitrogen is bubbled through thereaction mixture. Nitrogen blowing is continued for an additional 15minutes and the reaction mixture then diluted with 940 parts of xyleneto a solution containing 25% by weight of xylene. The resulting solutionhas a nitrogen content of 5.4% and a base number of 82 at pH of 4, thelatter being indicative of free amino groups.

A 789 gram portion of the above xylene solution (3 equivalents ofnitrogen) is heated to 150 C. at a pressure of 2 millimeters of mercuryto distill ofl xylene and is then mixed with 367 grams of heptylphenol(having a hydroxyl content of 8.3%; 1.8 equivalents). To this mixturethere is added 345 grams (4.5 equivalents) of barium oxide in smallincrements at -111 C. The mixture is heated at 90120 C. for 2.5 hoursand blown with carbon dioxide for 1.75 hours. It is diluted with gramsof xylene and then heated at C. for 3.5 hours. It is then diluted with20% by weight of xylene and filtered. The filtrate has a barium sulfateash content of 33.2%, a nitrogen content of 3.52% and a reflux basenumber of 134.

Example 31 To a mixture of 408 grams (2 equivalents) of heptylphenolhaving a hydroxy content of 8.3% and 264 grams of xylene there is added383 grams (5 equivalents) of barium oxide in small increments at 85 1 10C. Thereafter, 6 grams of water is added and the mixture is carbonatedat 100-130 'C. and filtered. The filtrate is heated to 100 'C. dilutedwith xylene to a 25 xylene solution. This solution has a barium sulfateash content of 41% and a reflux base number of 137.

Example 32 A mixture of 5,846 parts (4.0 equivalents) of a neutralcalcium sulfonate having a calcium sulfate ash content of 4.68% (66%mineral oil), 464 parts (2.4 equivalents) of heptylphenol, and 3.4 partsof water is heated to 80 C. whereupon 1,480 parts (19.2 equivalents) ofbarium oxide is added over a period of 0.6 hour. The reaction isexothermic and the temperature of the reaction mixture reaches 100 C.The mixture is heated to 150 C. and carbonated at this temperature.During the carbonation, 24 parts of barium chloride were added to themixture. Oil was removed from the reaction mixture during thecarbonation procedure. Carbonation is continued at this temperatureuntil the mixture has a base number (phe' nolphthalein) of 80. Octylalcohol (164 parts) and a filter aid are added to the mixture and themixture is filtered while hot. The filtrate is the desired overbasedbarium bright stock sulfonate having a barium sulfate ash content of26.42, a metal ratio of 4.6 and a reflux base number of 104.

27 Example 33 Following the procedure for preparing barium and calciumoverbased sulfonates exemplified above, sodium mahogany sulfonate (0.26equivalent), 1 equivalent of phenol, and 5.3 equivalents of strontiumoxide are carbonated until the reaction mixture is almost neutral. Theresulting overbased material is filtered, the filtrate being the desiredproduct and having a metal ratio of 4.6.

Example 34 A barium overbased carboxylic acid is prepared by carbonatinga mixture of 9.8 equivalents of barium hydroxide, 1 equivalent ofheptylphenol, and 0.81 equivalent of a polyisobutene substitutedsuccinic anhydride wherein the polyisobutenyl portion thereof has anaverage molecular Weight of 1,000.

Example 35 A mixture of 1,000 parts by weight of a polyisobutene havinga molecular weight of 1,000 and 90 parts of phosphorus pentasulfide isprepared at room temperature, heated to 260 C. over hours, andmaintained at this temperature for an additional 5 hours. The reactionmass is then cooled to 106 C. and hydrolyzed by treatment with steam atthis temperature for 5 hours. The hydrolyzed acid has a phosphoruscontent of 2.4%, a sulfur content of 2.8%. In a separate vessel, amixture of oil and barium hydroxide is prepared by mixing 2,200 parts ofa mineral oil and 1,150 parts of barium oxide at 88 C. and blowing themixture with steam for 3 hours at 150 C. To this mixture there is addedportionwise throughout a period of 3 hours, 1,060 parts of the abovehydrolyzed acid while maintaining the temperature at 145 150 C., andthen 360 parts of heptylphenol is added over a 1.5 hour period. Theresulting mixture is blown with carbon dioxide at the rate of 100 partsper hour for 3 hours at 150-157 C. The carbonated product is mixed with850 parts of a mineral oil and dried by blowing it with nitrogen at atemperature of 150 C. The dry product is filtered and the filtrate isdiluted with mineral oil to a solution having a barium sulfate ashcontent of 25%. The final solution has a phosphorus content of 0.48%, aneutralization number less than 5 (basic), a refiux base number of 109,and a metal ratio of 7.2.

Example 36 (a) To a mixture of 268 grams (1.0 equivalent) of oleylalcohol, 124 grams (0.6 equivalent) of heptylphenol, 988 grams ofmineral oil, and 160 grams of water there is added 168 grams (4.0equivalents) of lithium hydroxide monohydrate. The mixture is heated atreflux temperature for an hour and then carbonated at 150 C. until it issubstantially neutral. The filtration of this carbonated mixture yieldsa liquid having a lithium sulfate content of 12.7%.

(b) To a mixture of 1,614 parts (3 equivalents) of a polyisobutenylsuccinic anhydride prepared by the reaction of a chlorinatedpolyisobutene having an average chlorine content of 4.3% and an averageof 67 carbon atoms with maleic anhydride at about 200 (3., 4,313 partsof mineral oil, 345 parts 1.8 equivalents) of heptylphenol, and 200parts of water, at 80 C., there is added 1,038 parts (24.7 equivalents)of lithium hydroxide monohydrate over a period of 0.75 hour whileheating to 105 C. Isooctanol (75 parts) is added while the mixture isheated to 150 C. in about 1.5 hours. The mixture is maintained at150-170 C. and blown with carbon dioxide at the rate of 4 cubic feet perhour for 3.5 hours. The reaction mixture is filtered through a filteraid and the filtrate is the desired product having a sulfate ash contentof 18.9 and a metal ratio of 8.

Example 37 A thiophosphorus acid is prepared as set forth in Example 35above. A mixture of 890 grams of this acid (0.89 equivalent), 2,945grams of mineral oil, 445 grams of heptylphenol (2.32 equivalents), and874 grams of lithium hydroxide monohydrate (20.8 equivalents) formed byadding the metal base to the mineral oil solution of the acid and theheptylphenol over a 1.5 hour period maintaining the temperature atl001l0 C. and thereafter drying at C. for 2 hours, carbon dioxide isbubbled therethrough at the rate of 4 cubic feet per hour until thereaction mixture was slightly acidic to phenolphthalein, about 3.5hours, while maintaining the temperature within the range of 150-160 C.The reaction mixture is then filtered twice through a diatomaceous earthfilter. The filtrate is the desired lithium overbased thio-phosphorusacid material having a metal ratio of 6.3.

Example 38 (a) A reaction mixture comprising 2,442 grams (2.8equivalents) of strontium petrosulfonate, 3,117 grams of mineral oil,150 grams of isooctanol, and 910 grams of methanol is heated to 55 C.and thereafter 615 grams of strontium oxide (11.95 equivalents) is addedover a 10 minute period While maintaining the reaction at a temperatureof 5565 C. The mixture is heated an additional hour at this sametemperature range and thereafter blown with carbon dioxide at a rate of4 cubic feet per hour for about 3 hours until the reaction mixture wasslightly acidic to phenolphthalein. Thereafter, the reaction mixture isheated to C. and held there for about 1 hour while blowing the nitrogenat 5 cubic feet per hour. Thereafter, the product is filtered, thefiltrate being the desired overbased material having a metal ratio of3.8.

(b) To a mixture of 3,800 parts (4 equivalents) of a 50% mineral oilsolution of lithium petroleum sulfonate (sulfate ash of 6.27%), 460parts (2.4 equivalents) of heptylphenol, 1,920 parts of mineral oil, and300 parts of water, there is added at 70 C. 1,216 parts (28.9equivalents) of lithium hydroxide monohydrate over a period of 0.25hour. This mixture is stirred at 110 C. for 1 hour, heated to 15 0 C.over a 2.5 hour period, and blown with carbon dioxide at the rate of 4cubic feet per hour over a period of about 3.5 hours until the reactionmixture is substantially neutral. The mixture is filtered and thefiltrate is the desired product having a sulfate ash content of 25.23%and a metal ratio of 7.2.

Example 39 A mixture of alkylated benzene sulfonic acids and naphtha isprepared by adding 1,000 grams of a mineral oil solution of the acidcontaining 18% by weight mineral oil (1.44 equivalents of acid) and 222grams of naphtha. While stirring the mixture, 3 grams of calciumchloride dissolved in 90 grams of water and 53 grams of Mississippi lime(calcium hydroxide) is added. This mixture is heated to 97-99 C. andheld at this temperature for 0.5 hour. Then 80 grams of Mississippi limeare added to the reaction mixture with stirring and nitrogen gas isbubbled therethrough to remove water, while heating to 150 C. over a 3hour period. The reaction mixture is then cooled to 50 C. and grams ofmethanol are added. The resulting mixture is blown with carbon dioxideat the rate of 2 cubic feet per hour until substantially neutral. Thecarbon dioxide blowing is discontinued and the water and methanolstripped from the reaction mixture by heating and bubbling nitrogen gastherethrough. While heating to remove the water and methanol, thetemperature rose to 146 C. over a 1.75 hour period. At this point themetal ratio of the overbased material was 2.5 and the product is aclear, dark brown viscous liquid. This material is permitted to cool to50 C. and thereafter 1,256 grams thereof is mixed with 574 grams ofnaphtha, 222 grams of methanol, 496 grams of Mississippi lime, and 111grams of an equal molar mixture of isobutanol and amyl alcohol. Themixture is thoroughly stirred and carbon dioxide is blown therethroughat the rate of 2 cubic feet per hour for 0.5 hour. An additional 124grams of Mississippi lime is added to the mixture with stirring and theCO blowing continued. Two additional 124 grain increments of Mississippilime are added to the reaction mixture while continuing the carbonation.Upon the addition of the last increment, carbon dioxide is bubbledthrough the mixture for an additional hour. Thereafter, the reactionmixture is gradually heated to about 146 C. over a 3.25 hour periodwhile blowing with nitrogen to remove water and methanol from themixture. Thereafter, the mixture is permitted to cool to roomtemperature and filtered producing 1,895 grams of the desired overbasedmaterial having a metal ratio of 11.3. The material contains 6.8%mineral oil, 4.18% of the isobutanol-amyl alcohol and 30.1% naphtha.

Example 40 A mixture of 406 grams of naphtha and 214 grams of amylalcohol is placed in a three-liter flask equipped with reflux condenser,gas inlet tubes, and stirrer. The mixture is stirred rapidly whileheating to 38 C. and adding 27 grams of barium oxide. Then 27 grams ofwater are added slowly and the temperature rises to 45 C. Stirring ismaintained while slowly adding over 0.25 hours 73 grams of oleic acid.The mixture is heated to 95 C. with continued mixing. Heating isdiscontinued and 523 grams of barium oxide are slowly added to themixture. The temperature rises to about 115 C. and the mixture ispermitted to cool to 90 C. whereupon 67 grams of water are slowly addedto the mixture and the temperature rises to 107 C. The mixture is thenheated within the range of 107120 C. to remove water over a 3.3 hourperiod while bubbling nitrogen through the mass. Subsequently, 427 gramsof oleic acid is added over a 1.3 hour period while maintaining atemperature of 120125 C. Thereafter heating is terminated and 236 gramsof naphtha is added. Carbonation is commenced by bubbling carbon dioxidethrough the mass at two cubic feet per hour for 1.5 hours during whichthe temperature is held at 108-117 C. The mixture is heated under anitrogen purge to remove water. The reaction mixture is filtered twiceproducing a filtrate analyzing as follows: sulfate ash content, 34.42%;metal ratio, 3.3 The filtrate contains 10.7% amyl alcohol and 32%naphtha.

Example 41 A reaction mixture comprising 1,800 grams of a calciumoverbased petrosulfonic acid containing 21.7% by weight mineral oil,36.14% by weight naphtha, 426 grams naphtha, 255 grams of methanol, and127 grams of an equal molar amount of isobutanol and amyl alcohol areheated to 45 C. under reflux conditions and 148 grams of Mississippilime (commercial calcium hydroxide) is added thereto. The reaction massis then blown with carbon dioxide at the rate of 2 cubic feet per hourand thereafter 148 grams of additional Mississippi lime added.carbonation is continued for another hour at the same rate. Twoadditional 147 gram increments of Mississippi lime are added to thereaction mixture, each increment followed by about a 1 hour carbonationprocess. Thereafter, the reaction mass is heated to a temperature of 138C. while bubbling nitrogen therethrough to remove water and methanol.After filtration, 2,220 grams of a solution of the barium overbasedpetrosulfonic acid is obtained having a metal ratio of 12.2 andcontaining 12.5% by weight mineral oil, 34.15% by weight naphtha, and4.03% by weight of the isobutanol amyl alcohol mixture.

Example 42 (a) Following the procedure of Example 2 above, thecorresponding lead product is prepared by replacing the bariumpetrosulfonate with lead petroleum sulfonate (1 30 equivalent) andbarium oxide with lead oxide (25 equivalents).

(b) Following the procedure of Example 5(a) above, the correspondingoverbased sodium sulfonate is prepared by replacing the barium oxidewith sodium hydroxide.

The above examples illustrate various means for preparing overbasedmaterials suitable for conversion to the non-Newtonian colloidaldisperse systems utilized in the present invention. Obviously, it iswithin the skill of the art to vary these examples to produce anydesired overbased material. Thus, other acidic materials such asmentioned hereinbefore can be substituted for the CO S0 and acetic acidused in the above examples. Similarly, other metal bases can be employedin lieu of the metal base used in any given example. Or mixtures ofbases and/or mixtures of materials which can be overbased can beutilized. Similarly, the amount of mineral oil or other non-polar,inert, organic liquid used as the overbasing medium can be varied widelyboth during overbasing and in the overbased product.

The following examples illustrate the conversion of the Newtonianoverbased materials into non-Newtonian colloidal disperse systems byhomogenization with conversion agents.

Example I To 733 grams of the overbased material of Example 5(a) thereis added 179 grams of acetic acid and 275 grams of a mineral oil (havinga viscosity of 2000 SUS at 100 F.) at C. in 1.5 hours with vigorousagitation. The mixture is then homogenized at 150 C. for 2 hours and theresulting material is the desired colloidal disperse system.

Example II A mixture of 960 grams of the overbased material of Example 5(b), 256 grams of acetic acid, and 300 grams of a mineral oil (having aviscosity of 2000 SUS at F.) is homogenized by vigorous stirring at C.for 2 hours. The resulting product is a non-Newtonian colloidal dispersesystem of the type contemplated for use by the present invention.

The overbased material of Examples I and II can be converted without theaddition of additional mineral oil or if another inert organic liquid issubstituted for the mineral oil.

Example III A mixture of 150 parts of the overbased material of Example6, 15 parts of methyl alcohol, 10.5 parts of amyl alcohol, and 45 partsof water is heated under reflux conditions at 7l74 C. for 13 hourswhereupon the mixture gels. The gel is heated for 6 hours at 144 C.,diluted with 126 parts of the mineral oil of the type used in Example Iabove the diluted mixture heated to 144 C. for an additional 4.5 hours.The resulting thickened product is a colloidal disperse system. Again,it is not necessary that the material be diluted with mineral oil inorder to be useful. The gel itself which results from the initialhomogenization of the overbased material and the lower alkanol mixtureis a particularly useful colloidal disperse system for incorporatinginto resinous compositions.

Example IV A mixture of 1,000 grams of the product of Example 12, 80grams of methanol, 40 grams of mixed primary amyl alcohols (containingabout 65% by weight of normal amyl alcohol, 3% by weight of isoamylalcohol, and 32% by weight of 2-methyl-1-butyl alcohol) and 80 grams ofwater are introduced into a reaction vessel and heated to 70 C. andmaintained at that temperature for 4.2 hours. The overbased material isconverted to a gelatinous mass, the latter is stirred and heated at 150C. for a period of about 2 hours to remove substantially all thealcohols and water. The residue is a dark green gel, which is aparticularly useful colloidal disperse system.

3 1 Example V The procedure of Example IV is repeated except that 120grams of water is used to replace the water-alkanol mixture employed asthe conversion agent therein, Conversion of the Newtonian overbasedmaterial into the non-Newtonian colloidal disperse system requires abouthours of homogenization. The disperse system is in the form of a gel.

Example VI To 600 parts by weight of the overbased material of Example6, there is added 300 parts of dioctylphthalate, 48 parts of methanol,36 parts of isopropyl alcohol, and 36 parts of water. The mixture isheated to 70"-77 C. and maintained at this temperature for 4 hoursduring which the mixture becomes more viscous. The viscous solution isthen blown with carbon dioxide for 1 hour until substantially neutral tophenolphthalein. The alcohols and water are removed by heating toapproximately 150 C. The residue is the desired colloidal dispersesystem.

Example VII To 800 parts of the overbased material of Example 6, thereis added 300 parts of kerosene, 120 parts of an alcohol: Water mixturecomprising 64 parts of methanol, 32 parts of water and 32 parts of theprimary amyl alcohol mixture of Example IV. The mixture is heated to 75C. and maintained at this temperature for 2 hours during which time theviscosity of the mixture increases. The water and alcohols are removedby heating the mixture to about 150 C. while blowing with nitrogen for 1hour. The residue is the desired colloidal disperse system having theconsistency of a gel.

Example VIII A mixture of 340 parts of the product of Example 6, 68parts of an alcohohwater solution consisting of 27.2 parts of methanol,20.4 parts of isopropyl alcohol and 20.4 parts of Water, and 170 partsof heptane is heated to 65 C. During this period, the viscosity of themixture increases from an initial value of 6,250 to 54,000.

The thickened colloidal disperse system is further neutralized byblowing the carbon dioxide at the rate of 5 lbs. per hour for 1 hour.The resulting mass is found to have a neutralization number of 0.87(acid to phenolphthalein indicator).

Example IX The procedure of Example VIII is repeated except that thecalcium over-based material of Example 6 is replaced by an equivalentamount of the cadmium and barium overbased material of Example 17.Xylene (200 parts) is used in lieu of the heptane and the furthercarbonation step is omitted.

Example X A mixture of 500 parts of the overbased material of Example 6,312 parts of kerosene, 40 parts of methylethyl ketone, parts ofisopropyl alcohol, and 50 parts of water is prepared and heated to 75 C.The mixture is maintained at a temperature of 70-75 C. for 5 hours andthen heated to 150 C. to remove the volatile components. The mixture isthereafter blown with ammonia for minutes to remove most of the finaltraces of volatile materials and thereafter permitted to cool to roomtemperature. The residue is a brownish-tan colloidal disperse system inthe form of a gel.

Example XI A mixture of 500 parts of the product of Example 6, 312 partsof kerosene, parts of acetone, and 60 parts of water is heated to refluxand maintained at this temperature for 5 hours with stirring. Thetemperature of the material is then raised to about 155 C. whileremoving the volatile components. The residue is a viscous gel-likematerial which is the desired colloidal disperse system.

Example XII The procedure of Example XI is repeated with thesubstitution of 312 parts of heptane for the kerosene and 60 parts ofwater for the acetone-water mixture therein. At the completion of thehomogenization, hydrogen gas is bubbled through the gel to facilitatethe removal of water and any other volatile components.

Example XIII A mixture of 500 parts of the overbased material of Example5(a) and 312 parts of heptane is heated to C. whereupon 149 parts ofglacial acetic acid (99.8% by weight) is added dropwise over a period of5 hours. The mixture is then heated to 150 C. to remove the volatilecomponents. The resulting gel-like material is the desired colloidaldisperse system.

Example XV The procedure of Example XIV is repeated except that 232parts of boric acid is used in lieu of the acetic acid. The desired gelis produced.

Example XVI The procedure of Example XII is repeated except that thewater is replaced by 40 parts of methanol and 40 parts of diethylenetriamine. Upon completion of the homogenization, a gel-like colloidaldisperse system is produced.

Example XVII A mixture of 500 parts of the product of Example 6 and 300parts of heptane is heated to 80 C. and 68 parts of anthranilic acid isadded over a period of 1 hour while maintaining the reaction temperaturebetween 80 and C. The reaction mixture is then heated to C. over a 2hour period and then blown with nitrogen for 15 minutes to remove thevolatile components. The resulting colloidal disperse system is amoderately stiff gel.

Example XVIII The procedure of Example XVIII is repeated except that theanthranilic acid is replaced by 87 parts of adipic acid. The resultingproduct is very viscous and is the desired colloidal disperse system.This gel can be diluted, if desired, with mineral oil or any of theother materials said to be suitable for disperse mediums hereinabove.

Example XIV A mixture of 500 parts of the product of Example 8 and 300parts of heptane is heated to 80 C. whereupon 148 parts of glacialacetic acid is added over a period of 1 hour while maintaining thetemperature within the range of about 80-88 C. The mixture is thenheated to 150 C. to remove the volatile components. The residue is aviscous gel which is useful for incorporation into the polymeric resinsof the present invention. It may also be diluted with a materialsuitable as a disperse medium to facilitate incorporation into resinouscompositions.

Example XX A mixture of 300 parts of toluene and 500 parts of anoverbased material prepared according to the procedure of Example 7 andhaving a sulfate ash content of 41.8% is heated to 80 C. whereupon 124parts of glacial acetic acid is added over a period of 1 hour. Themixture is then heated to 175 C. to remove the volatile componehts.During this heating, the reaction mixture becomes very viscous and 380parts of mineral oil is added to facilitate the removal of the volatilecomponents. The resulting colloidal disperse system is a very viscousgrease-like material.

Example XXI A mixture of 700 parts of the overbased material of Example5(b), 70 parts of water, and 350 parts of toluene is heated to refluxand blown with carbon dioxide at the rate of 1 cubic foot per hour for 1hour. The reaction product is a soft gel.

Example XXII The procedure of Example XVIII is repeated except that theadipic acid is replaced by 450 grams of di(4- methyl-amyl)phosphorodithioic acid. The resulting material is a gel.

Example XXIII The procedure of Example XVI is repeated except that themethanol-amine mixture is replaced by 250 parts of a phosphorus acidobtained by treating with steam at 150 C. the product obtained byreacting 1000 parts of polyisobutene having a molecular weight of about60,000, with 24 parts of phosphorus pentasulfide. The product is aviscous brown gel-like colloidal disperse system.

Example XXIV The procedure of Example XX is repeated except that theoverbased material therein is replaced by an equivalent amount of thepotassium overbased material of Example 18 and the heptane is replacedby an equivalent amount of toluene.

Example XXV The overbased material of Example 6 is isolated as a drypowder by precipitation out of a benzene solution through the additionthereto of acetone. The precipitate is washed with acetone and dried.

A mixture of 45 parts of a toluene solution of the above powder (364parts of toluene added to 500 parts of the powder to produce a solutionhaving a sulfate ash content of 43%), 36 parts of methanol, 27 parts ofwater, and 18 parts of mixed isomeric primary amyl alcohols (describedin Example IV) is heated to a temperature within the range of 7075 C.The mixture is maintained at this temperature for 2.5 hours and thenheated to remove the alkanols. The resulting material is a colloidaldisperse system substantially free from any mineral oil. If desired, thetoluene present in the colloidal disperse system as the disperse mediumcan be removed by first diluting the disperse system with mineral oiland thereafter heating the diluted mixture to a temperature of about 160C. whereupon the toluene is vaporized.

Example XXVI Calcium overbased material similar to that prepared inExample 6 is made by substituting xylene for the mineral oil usedtherein. The resulting overbased material has a xylene content of about25% and a sulfate ash content of 39.3%. This overbased material isconverted to a colloidal disperse system by homogenizing 100 parts ofthe overbased material with 8 parts of methanol, 4 parts of the amylalcohol mixture of Example IV, and 6 parts of water. The reaction massis mixed for 6 hours while maintaining the temperature at 7578 C.Thereafter, the disperse system is heated to remove the alkanols andwater. If desired, the gel can be diluted by the addition of mineraloil, toluene, xylene, or any other suitable disperse medium.

34 Example XXVII A solution of 1,000 grams of the gel-like colloidaldisperse system of Example III is dissolved in 1,000 grams of toluene bycontinuous agitation of these two components for about 3 hours. Amixture of 1,000 grams of the resulting solution, 20 grams of water, and20 grams of methanol are added to a 3-liter flask. Thereafter, 92.5grams of calcium hydroxide is slowly added to the flask with stirring.An exothermic reaction takes place raising the temperature to 32 C. Theentire reaction mass is then heated to about 60 C. over a 0.25 hourperiod. The heated mass is then blown with carbon dioxide at the rate of3 standard cubic feet per hour for 1 hour while maintaining thetemperature at 6070 C. At the conclusion of the carbonation, the mass isheated to about 150 C. over a 0.75 hour period to remove water,methanol, and toluene. The resulting product is a clear, light browncolloidal disperse system in the form of a gel. In this manneradditional metal containing particles are incorporated into thecolloidal disperse system.

At the conclusion of the carbonation step and prior to removing thewater, methanol, and toluene, more calcium hydroxide could have beenadded to the mixture and the carbonation step repeated in order to addstill additional metal-containing particles to the colloidal dispersesystem.

Example XXVIII A mixture of 1200 grams of the gel produced according toExample III, 600 grams of toluene, and 48 grams of water is blown withcarbon dioxide at 2 standard cubic feet per hour while maintaining thetemperature at 55- 65 C. for 1 hour. The carbonated reaction mass isthen heated at 150 C. for 1.75 hours to remove the water and toluene.This procedure improves the texture of the colloidal disperse systemsand converts any calcium oxide or calcium hydroxide present in the gelproduced according to Example III into calcium carbonate particles.

Example XXIX A mixture comprising 300 grams of water, grams of the amylalcohol mixture identified in Example IV above, 100- grarns of methanol,and 1000 grams of a barium overbased oleic acid, prepared according tothe general technique of Example 3 by substituting oleic acid for thepetrosulfonic acid used therein, and having a metal ratio of about 3.5is thoroughly mixed for about 2.5 hours while maintaining thetemperature within the range of from about 72-74 C. At this point theresulting colloidal disperse system was in the form of a very soft gel.This material was then heated to about 150 C. for a 2 hour period toexpel methanol, the amyl alcohols, and water. Upon removal of theseliquids, the colloidal disperse system was a moderately stifi, gel-likematerial.

Example XXX A dark brown colloidal disperse system in the form of a verystiff gel was prepared from the product of Example 39 using a mixture of64 grams of methanol and grams of water as the conversion agent toconvert 800 grams of the overbased material. After the conversionprocess, the resulting disperse system is heated to about 150 C. toremove the alcohol and water.

Example XXXI 1000 grams of the overbased material of Example 40 isconverted to a colloidal disperse system by using as a conversion agenta mixture of grams of methanol and 300 grams of water. The mixture isstirred for 7 hours at a temperature within the range of 7280 C. At theconclusion of the mixing, the resulting mass is heated gradually to atemperature of about C. over a 3 hour period to remove all volatileliquid contained therein. Upon removal of all volatile solvents, a tanpowder was obtained. By thoroughly mixing this tan powder to a suitableorganic liquid such as naphtha, it is again transformed into a colloidaldisperse system.

Example XXXII Overbased material converted Example No. to colloidaldisperse system XXXIII Example XXXIV Example 21 XXXV Example 23 XXVIExample 24(a) XXXVII Example 28 XXXVIH Example 31 XXXIX Example 39 XLExample 40 The preparation of other non-Newtonian colloidal dispersesystems useful in the compositions of this invention are disclosed incopending applications Ser. No. 535,048 filed Mar. 17, 1966, and Ser.No. 535,693 filed Mar. 21,

The change in rheological properties associated with conversion of aNewtonian overbased material into a non-Newtonian collodial dispersesystem is demonstrated by the Brookfield Viscometer data derived fromoverbased materials and colloidal disperse systems prepared therefrom.In the following samples, the overbased material and the colloidaldisperse systems are prepared according to the above-discussed andexemplified techniques. In each case, after preparation of the overbasedmaterial and the colloidal disperse system, each is blended withdioctylphthalate (DOP) so that the compositions tested in the viscometercontain 333% by weight DOP (Samples A, B, and C) or 50% by weight DOP(Sample D). In Samples A-C, the acidic material used in preparing theoverbased material is carbon dioxide while in Sample D, acetic acid isused. The samples each are identified by two numbers, (1) and (2). Thefirst is the overbased materialDOP composition and the second thecolloidal disperse systemDOP composition. The overbased materials of thesamples are further characterized as follows:

Sample A Calcium overbased petrosulfonic acid having a metal ratio ofabout 12.2.

Sample B Barium overbased oleic acid having a metal ratio of about 3.5.

Sample C Barium overbased petrosulfonic acid having a metal ratio ofabout 2.5.

Sample D Calcium overbased commercial higher fatty acid mixture having ametal ratio of about 5.

The Brookfield Viscometer data for these compositions is tabulatedbelow. The data of all samples is collected at C.

BROOKFIELD vIsooMETER DATA The following examples are illustrative ofthe polymeric compositions of the present invention containing thecolloidal disperse systems. A variety of resinous materials are utilizedin the examples. In some instances, Brookfield viscometer data is givenon the resulting compositions to demonstrate the non-Newtoniancharacteristics of the polymeric compositions containing thenon-Newtonian colloidal disperse systems. The use of BrookfieldViscosities for determining the non-Newtonian characteristics of a givenplastic composition is the subject of an article A Method for theInterpretation of Brookfield Viscosities" by R. L. Bowles et al., andpublished in Modern Plastics, volume 33, No. 3, pages 140148 (1955).

The following polymeric compositions are prepared by blending theindicated components in a Hobart Mixer.

COMPONENTS OF THE COMPOSITION [Parts by weight] Example No. PVC 1 DOP 2Disperse System 100 5 parts-Ex. III. 80 10 parts-Ex. III. 100 80 5partsEx. XXXI. 100 80 5 partsB atrium-containing disperse system.

1 Commercially available pelletized polyvinyl chloride resin from B.FGoodrich Chemical Co. as Geon 121.

2 Dioetyl phthalate-plasticizer.

3 Disperse system prepared from a barium overbased petroleum sulionicacid (metal ratio-2.5)

B ROOKFIELD VISOOMETER DATA [Centipoises] A B C D This data vividlydemonstrates the marked apparent viscosity differences associated withan increase in the rate of shear (r.p.m.).

The following epoxy resin compositions are prepared by blending theindicated materials:

COMPONENTS OF THE COMPOSITION Parts by weight] Example No. Epoxy ResinDOP Disperse System Commercially available epoxy resin from ShellChemical Co. as Epon 828.

2 The disperse system of Example XXXIII.

B ROOKFIELD VISCOMETER DATA {Centipoisesl R.p.m E F G H Example ICold-dip polyvinyl chloride plastisols having the following compositionsare prepared by blending the appro- Composition consisting of product oftype according to Example III and 33% by weight DOP.

Composition consisting of product of type according to Example III and30% by Weight xylene.

Comp0sition consisting of product of type according to Example III and30% by weight Stoddard Solvent.

BROOKFIELD VISCOMETER DATA A mixture of 3,410 grams of petrosulfonicacid equivalents) and 2048 grams of naphtha are added to a 12 literflask fitted with stirrer, reflux condenser, ga inlet tube, andthermometer. This mixture is heated to 95 C. under reflux conditions anda solution of 283 grams of calcium chloride in 283 grams of water isadded slowly to the reaction mass over approximately a 1 hour period.The mixing was continued for another 0.5 hour and thereafter 278 grams(7.5 equivalents) of Mississippi lime was added slowly to the mass andstirring was maintained for an additional 0.5 hour. The mass was thenheated to remove water while bubbling nitrogen gas therethrough tofacilitate the water removal. After the water removal step, the mass iscooled to 60 C. and 580 grams of methanol are added which resulted in afurther drop of the temperature to 50 C. Thereafter, the reaction massis maintained at a temperature of 45-60 C. while blowing carbon dioxidetherethrough at 4 cubic feet per hour for 1 hour. Carbonation isterminated and the temperature is elevated to about 150 C. with anitrogen purge to remove water and methanol. After filtering, 4,795grams of material was recovered in the form of a clear dark brown liquidhaving a metal ratio of 2.5 and containing 21.07% mineral oil (from thepetrosulfonic acid starting material) and 36.14% naphtha.

Thirty-six hundred grams of the material produced above, 1,706 gramsnaphtha, and 510 grams of methanol are added to a 12 liter flaskequipped as before. The mixture is heated to about 45 C. and 295 gramsof calcium hydroxide are added thereto. While maintaining thetemperature within the range of 4550 C. carbon dioxide is blown throughthe mass at the rate of 3.5 cubic feet per hour for 0.5 hour. Anadditional 295 grams of calcium hydroxide is added and the carbonationcontinued for an additional hour. Again, 295 grams of calcium hydroxideare added and carbonation is continued for another hour with stillanother 295 gram portion of calcium hydroxide then being added followedby an additional 275 hours of carbonation. A nitrogen purge and heatingto about 150 C. removes the methanol and water from the product. Acommercial filter aid material is added to the mass and the whole wasfiltered yielding 5,347 grams filtrate. This filtrate consists of aclear dark brown liquid and is a calcium overbased petrosulfonic acidmaterial having a metal ratio of 11.95 and an oil content of 11% and anaphtha content of 45%, and a barium sulfate ash content of 37.43%.

A mixture comprisng 500 grams of the overbased material produced above,500 grams of naphtha, 50 grams of water, and 40 grams of methanol areadded to a 3 liter flask equipped with a reflux condenser and stirrer.This mixture is heated to 73 C. over a 1 hour period and maintained at7274 C. for an additional two hours with continued mixing. The resultingmixture is then transferred to a Hobart mixer and 420 grams ofdioctylphthalate are added thereto. Thorough mixing is conducted over a2 hour period while raising the temperature to about 155 C. to removethe methanol, water, and naphtha. The resulting colloidal dispersesystem consists of a soft gel-like material having a sulfate ash contentof 27.06%, dioctylphthalate content of 60.3%, and an oil content of7.9%.

The colloidal disperse system thus produced is incorporated into amixture of commercially available epoxy resins (270 grams of Epon 828),240 grams of dioctylphthalate, and 60 grams of the disperse system.Because of the high dilution of this particular colloidal disperse,i.e., about 70% of the disperse system is dioctylphthalate and mineraloil, the amount of metal-containing particles therein is greatlyreduced. In fact, the calcium content of the overall disperse system isless than 8%. Accordingly, the Brookfield Viscosity data indicatesdecreased effectiveness in altering the viscosity of the resinousmaterial. However, if the dioctylphthalate content of the dispersesystem is reduced by 40 to 60%, a much more effective modification ofthe viscosity is achieved.

Example K A resinous composition is prepared by blending 180 parts ofthe commercial epoxy resin of Example J, 180 parts of dioctylphthalate,and 40 parts of the colloidal disperse system of the type prepared inExample III except that an equivalent amount of acetic acid is used asthe conversion in lieu of the alkanol-water mixture. BrookfieldViscometer data shows centipoise values of 4,400; 3,100; 1,970; and1,500 for r.p.m. values of 2, 4, 10, and 20. A control batch of 120parts each of the epoxy resin and dioctylphthalate exhibit cps. valuesof 700, 675, 630, and 620 at the same r.p.m. values under identicalconditions.

Example L A substantially oil-free disperse system is prepared byconverting an overbased calcium petrosulfonic acid material (which wasformed in a naphtha solution of the acid is shown in Example I) with analkanol-water mixture as a conversion agent. The alkanol-water mixtureconsisted of parts water, 60 parts methanol, and 60 parts isopropanol.Conversion is conducted in the presence of 570 parts ofdiisodecylphthalate. Upon completion of the conversion, the volatilematerials are removed from the resulting mass by heating for a period of2 hours at about C. The resulting disperse system comprises about equalweights of diisodecylphthalate and the converted overbased petrosulfonicacid material in the form of a light-brown stilt gel having a calciumsulfate ash content of about 36%. This gel-like material is then mixedwith dioctylphthalate in a weight ratio of gel to dioctylphthalate of100:50.

The mixture is incorporated into the commercially available liquidpolysulfide material used as a sealant in an amount of polysulfide resinto the mixture of 120218. Brookfield Viscometer tests show cps. valuesof 64,000; 56,000; 49,600; and 43,200 at 2, 4, 10, and 20 r.p.m.

Example M Barium-overbased oleic acid (metal ratio of about 3.5) isdissolved in naphtha to form 1,000 parts of a solution containing about57.6% of the naphtha. This solution and 100 parts of isopropanol aremixed and thereafter a solution of 100 parts of water containing 2.85parts of a 50% caustic solution is added thereto. The material isthoroughly mixed over a period of about 4 hours under reflux conditionsat a temperature of 7277 C. A light yellow disperse material results andhas the consistency of a gel. Subsequently, 576 parts ofdioctylphthalate is added to the disperse system with mixing whilemaintaining the temperature at about 5560 C. The temperature is thenraised to about C. for about 2 hours to remove the naphtha, water, andalcohols.

The resulting mixture is incorporated in the same liquid polysulfidematerial of Example M in the same weight ratio. Brookfield Viscometertests show cps. values of 128,000; 100,000; 72,000; and 59,200.

Example N A disperse system of the type produced in Example III is mixedwith xylene so that the resulting mixture contains about 30% by Weightxylene. This mixture is added to the polysulfide material of Example Min same weight ratio. Centipoise values of the resulting polymericcompositions are 32,000; 2 8,000; 27,200; and 26,400.

39 Example A polymeric structural caulk comprising as the major resinouscomponent about 50% by weight of a liquid polysulfide resin (LP-12 soldby Thiokol Chemical Company) exhibits centipoise values of 440,000;296,000; 194,000; and 155,000 in Brookfield Viscometer tests at 2, 4,10, and 20 rpm. A colloidal disperse system of the type described inExample 3 is blended with another portion of the identical caulk in anamount equal to 10% by weight based on the weight of the polysulfidepolymer. At the r.-p.m. values given above, the resulting caulk displayscps. values of 1,100,000; 700,000; 400,000; and 200,000.

Example P A white architectural caulk containing as the only majorpolymeric resin about 25% by weight of a commercially availablepolymercaptan resin is blended with a disperse system of the typeaccording to Example 3 in an amount of 5% and by weight based on theweight of the polymercaptan.

Example Q A butyl rubber caulk containing about 36% by Weight butylrubber as the only major polymeric resinous component is blended with10% by weight of the disperse system of Example III based on the weightof the butyl rubber.

Example R A disperse system is incorporated into a rigid polyvinylchloride resin according to the following technique. The commerciallyavailable rigid polyvinyl chloride (Geon 103 EP) in an amount of 400parts is added to a high speed blender operated at 5000 rpm. until thetemperature rises to about 98 C. A previously mixed compositioncomprising 20 parts of disperse system of Example III, 2 parts ofcalcium stearate, 4 parts parafiin wax, and 16 parts of a stabilizer forthe polyvinyl chloride resin is added to the polyvinyl chloride and thehigh-speed mixing is continued while raising the temperature of themixture to about 120 C. The resulting polymeric composition isparticularly adapted to extrusion processes.

Following the technique, the same type of disperse system isincorporated into similar rigid polyvinyl chloride formulations in anamount of 5, 7.5, and 10 parts by weight based on the weight of thepolyvinyl chloride present therein. The remainder of the composition isas follows: polyvinyl chloride-400 parts; stabilizers2 parts; titaniumdioxide-5 parts; and carbon black-2 parts.

Another polyvinyl chloride formulation is prepared comprising 100 partspolyvinyl chloride, 2 parts of the same stabilizer, 5 parts of acommercial polyvinyl chloride processing aid, 2 parts calcium stearate,0.7 part parafiin wax, 5 parts titanium dioxide, and 0.2 part of carbonblack.

The latter composition and the composition containing 5 parts of thedisperse system, 2 parts of stabilizer, 5 parts of titanium dioxide, 2parts carbon black, and 100 parts polyvinyl chloride are both used toextrude tubing. To extrude lbs. of the polyvinyl chloride formulationsof the prior art in one hour requires an extruder screwspeed of about 95rpm. while the same amount of the formulation containing the colloidaldisperse system requires a screw-speed of only 68 r.p.m. Or, fromanother viewpoint, a screw-speed of 70 rpm. extrudes about 11.5 lbs. ofprior art material per hour and about 15.5 lbs. of the polyvinylchloride formulation of the present invention. Moreover, the formulationof the present invention requires a total of 5 parts by weight of thecolloidal disperse system to replace 7.7 parts by weight of theprocessing aids, lubricants, etc. of the prior art. In other words, theamount of additive used in the prior art is reduced by about 35% on aweight basis without any loss in the quality of product and asubstantial gain in extrusion rate.

Example S A resinous composition is prepared by mixing parts ofpelletized polyvinyl chloride, 100 parts of dioctylphthalate, and 7.5parts of the disperse system of Example IX.

Example T A composition similar to that of Example S is prepared byreplacing the disperse system therein with the same weight of thedisperse system of Example XXV.

Example U Example Polymeric Resin Plasticizer V Polyvinyl acetateDieyclohexylphthalate.

W Cellulose nitrate Di-(2-ethylhexyl)phthalate. X Cellulose acetateDiethylphthalate.

Y Polyethylene Dicyclohexylphthalate.

Additional conventional additives can also be present in thesecompositions such as fillers, stabilizers, pigments, etc.

Example Z A polymeric composition is prepared following the technique ofExample S but substituting an equivalent amount of the disperse systemof Example XXXVII for that of Example IX.

Example AA A barium-overbased oleic acid prepared in naphtha and freefrom mineral oil is converted to a disperse system using anisopropanol-water mixture (200 parts isopropanol600 parts water) as theconversion agent. Thereafter, the disperse system is mixed withdioctylphthalate and heated to about C. to expel water, isopropanol, andnaphtha. The resulting mixture consists of 25 parts by weightdioctylphthalate and has a barium sulfate ash content of about 45%.Additional dioctylphthalate is added to give a total dioctylphthalatecontent of about 70 parts.

(A) A polymeric composition containing 77 parts of amercaptan-terminated polybutadiene-acrylonitrile copolymer, 19 parts ofan epoxy resin (Epon 828), and 4.8 parts of thedioctylphthalate-containing colloidal disperse system prepared above itsprepared by blending these components. The resulting compositionexhibits centipoise values of 114,000; 102,000; 84,400; and 74,800 asdetermined from the Brookfield Viscometer at 2, 4, l0, and 20 rpm.

(B) A similar composition is prepared using 84 parts of acarboxyl-terminated polybutadiene-acrylonitrile copolymer, 12 parts ofthe same epoxy resin, and 4.8 parts of the samedioctylphthalate-containing disperse system. At the same rpm. values, itexhibits centipoise values of 222,000; 201,000; 171,200; and 144,800.

Example BB A commercially available polyurethane resin (Wyandotte WUC3006-T) is blended with a colloidal disperse system consisting of 2parts by weight of the dioctylphthalate-containing disperse system ofExample AA and 1 part of the disperse system of Example II. The weightratio of polyurethane resin to the disperse sys-

